KR20190119631A - Electrolytic electrode, laminated body, wound body, electrolytic cell, electrolytic cell manufacturing method, electrode updating method, laminated body updating method and winding body manufacturing method - Google Patents

Abstract

The present invention relates to an electrode for electrolysis, a laminate, a wound body, an electrolytic cell, a method for producing an electrolytic cell, an method for updating an electrode, a method for updating a laminate, and a method for producing a wound body. The electrode for electrolysis which concerns on one aspect of this invention is 48 mg / cm <2> or less in mass per unit area, and the force applied per unit mass and unit area is 0.08 N / mg * cm <2> or more.

Description

Electrolytic electrode, laminated body, wound body, electrolytic cell, electrolytic cell manufacturing method, electrode updating method, laminated body updating method and winding body manufacturing method

The present invention relates to an electrode for electrolysis, a laminate, a wound body, an electrolytic cell, a method for producing an electrolytic cell, an method for updating an electrode, a method for updating a laminate, and a method for producing a wound body.

In electrolysis of aqueous alkali metal chloride solutions such as saline and electrolysis of water (hereinafter referred to as "electrolysis"), a method using a diaphragm, more specifically an electrolytic cell having an ion exchange membrane or a microporous membrane, is used. In most cases, this electrolytic cell includes electrolytic cells connected in series in a large number. Electrolysis is performed through a diaphragm between each electrolysis cell. In the electrolytic cell, the cathode chamber having the cathode and the anode chamber having the anode are arranged in front and back relationship through a partition wall (back plate) or through press pressure, bolting, or the like.

The positive electrode and negative electrode currently used for these electrolyzers are fixed by methods, such as welding and sandwiching, respectively, in an anode chamber and a cathode chamber of an electrolysis cell, are stored, and are conveyed to a customer. On the other hand, the diaphragm is stored by itself wrapped in a pipe made of vinyl chloride or the like and transported to a customer. The customer lists the electrolytic cells on the frame of the electrolytic cell and assembles the electrolytic cell by sandwiching a diaphragm between the electrolytic cells. In this way, the electrolytic cell is manufactured and the electrolytic cell assembly of the customer is performed. As a structure applicable to such an electrolytic cell, Patent Literatures 1 and 2 disclose structures in which a membrane and an electrode are integrated.

Patent Document 1: Japanese Patent Laid-Open No. 58-048686 Patent Document 2: Japanese Patent Laid-Open No. 55-148775

When the electrolytic operation is started and continued, various components deteriorate due to various factors, the electrolytic performance is lowered, and each component is replaced at some point. The diaphragm can be easily updated by taking out between the electrolytic cells and inserting a new diaphragm. On the other hand, since the positive electrode and the negative electrode are fixed to the electrolytic cell, when the electrode is renewed, the electrolytic cell is taken out of the electrolytic cell, taken out to the dedicated update factory, and the fixing of the welding or the like is removed to remove the old electrode and install a new electrode. There is a problem that a very complicated work of fixing by, for example, welding, transporting to an electrolytic plant, and returning to an electrolytic cell occurs. Here, although it is considered to use a structure in which the diaphragm and the electrode described in Patent Literatures 1 and 2 are integrated by thermocompression is used for the renewal, the structure can be manufactured at the laboratory level relatively easily, although the electrolytic cell of the actual commercial size can be manufactured. (E.g., 1.5 m in length and 3 m in width) is not easy to manufacture. In addition, electrolytic performance (electrolytic voltage, current efficiency, salt concentration in caustic soda) and durability are remarkably poor, and chlorine gas and hydrogen gas are generated on the electrode at the interface with the diaphragm. It is not usable practically.

This invention is made | formed in view of the subject which the said prior art has, and the following electrolytic electrode, laminated body, winding object, electrolytic cell, manufacturing method of an electrolytic cell, an electrode update method, an update method of a laminated body, and manufacture of a winding object It is an object to provide a method.

(First purpose)

Electrolytic electrode, laminated body which can simplify transportation and handling, and can greatly simplify the operation | movement at the time of starting a new electrolytic cell, or updating a deteriorated electrode, and can also maintain or improve electrolytic performance. And to provide a wound body.

(Second purpose)

An object of this invention is to provide the laminated body which can improve the work efficiency at the time of electrode update in an electrolytic cell, and can express the outstanding electrolytic performance after an update.

(Third purpose)

The present invention is another object of the present invention to provide a laminate which can improve the work efficiency at the time of electrode update in an electrolytic cell and can express excellent electrolytic performance even after the update from a second viewpoint. do.

(Fourth purpose)

An object of this invention is to provide the electrolytic cell, the manufacturing method of an electrolytic cell, and the update method of a laminated body which are excellent in electrolytic performance and can prevent damage of a diaphragm.

(5th purpose)

An object of this invention is to provide the manufacturing method of an electrolytic cell, the method of updating an electrode, and the manufacturing method of a wound body which can improve the working efficiency at the time of electrode update in an electrolytic cell.

(Sixth purpose)

Another object of the present invention is to provide a method for producing an electrolytic cell which can improve the working efficiency at the time of electrode update in an electrolytic cell from a viewpoint different from the fifth object.

(7th purpose)

Another object of the present invention is to provide a method for producing an electrolytic cell which can improve the working efficiency at the time of electrode update in the electrolytic cell from a viewpoint different from the above-mentioned fifth and sixth objects.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve 1st objective, the present inventors produced the electrolytic electrode which is small in mass per unit area, and can adhere | attach with diaphragm, such as an ion exchange membrane and a microporous membrane, and deteriorated electrode with weak force. It is easy to transport, handle, and can greatly simplify the operation when starting a new electrolytic cell or updating a deteriorated part, and can significantly improve the performance compared with the electrolytic performance of the prior art. In addition, the present invention has been completed by discovering that the update operation can be made equivalent to or improved in the electrolytic performance of a conventional electrolytic cell which is complicated.

That is, this invention includes the following.

[1] An electrolytic electrode having a mass per unit area of 48 mg / cm 2 or less and a force applied per unit mass and unit area of 0.08 N / mg · cm 2 or more.

[2] The electrolytic electrode according to [1], wherein the electrolytic electrode includes an electrolytic electrode substrate and a catalyst layer, and the thickness of the electrolytic electrode substrate is 300 µm or less.

[3] The electrode for electrolysis according to [1] or [2], wherein a ratio measured by the following method (3) is 75% or more.

[Method (3)]

On both sides of the membrane of the perfluorocarbon polymer into which the ion exchanger was introduced, a membrane (170 mm long) coated with inorganic particles and a binder, and an electrode sample for electrolysis (130 mm long) were laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 145 mm) so that the electrode sample for electrolysis in the laminate is the outer side, and the laminate and the pipe are placed. A membrane in which inorganic particles and a binder are applied to both surfaces of the membrane of the perfluorocarbon polymer into which the ion exchanger is introduced, after being sufficiently immersed in pure water and removing the excess water adhering to the laminate surface and the pipe, The ratio (%) of the area of the part where the electrolytic electrode sample is in close contact is measured.

[4] The electrode for electrolysis according to any one of [1] to [3], which has a porous structure and has a porosity of 5 to 90%.

[5] The electrode for electrolysis according to any one of [1] to [4], which has a porous structure and has a porosity of 10 to 80%.

[6] The electrode for electrolysis according to any one of [1] to [5], in which the thickness of the electrode for electrolysis is 315 µm or less.

[7] The electrode for electrolysis according to any one of [1] to [6], wherein a value measured by the following method (A) for the electrode for electrolysis is 40 mm or less.

[Method (A)]

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, a sample obtained by laminating an ion exchange membrane and the electrolytic electrode was wound and fixed on a curved surface of a vinyl chloride core material having an outer diameter of φ 32 mm, and left standing for 6 hours. Later, when the electrolytic electrode was separated and placed on a horizontal plate, the heights L ₁ and L ₂ in the vertical direction at both ends of the electrolytic electrode were measured, and these average values were measured.

[8] The ventilation resistance when the electrode for electrolysis is 50 mm x 50 mm and the temperature is 24 deg. C, the relative humidity is 32%, the piston speed is 0.2 cm / s, and the air flow rate is 0.4 cc / cm2 / s. The electrode for electrolysis as described in any one of [1]-[7] which is kPa * s / m or less.

[9] The electrolytic electrode according to any one of [1] to [8], in which the electrode contains at least one element selected from nickel (Ni) and titanium (Ti).

[10] A laminate comprising the electrode for electrolysis according to any one of [1] to [9].

[11] A wound body comprising the electrode for electrolysis according to any one of [1] to [9], or the laminate according to [10].

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the 2nd objective, by the laminated body provided with the electrode which adhere | attaches with a weak force, such as a diaphragm, such as an ion exchange membrane and a microporous membrane, and a deteriorated conventional electrode, The present invention has been completed by discovering that transportation and handling can be facilitated, the operation of starting a new electrolytic cell or updating a deteriorated component can be greatly simplified, and the electrolytic performance can be maintained or improved.

That is, this invention includes the following aspects.

[2-1]

An electrolytic electrode,

Diaphragm or feeder in contact with the electrolytic electrode

And

The laminated body whose force per unit mass and unit area of the said electrode for electrolysis with respect to the said diaphragm or feeder is less than 1.5 N / mg * cm <2>.

[2-2]

The laminated body as described in [2-1] whose force per unit mass and unit area of the said electrode for electrolysis with respect to the said diaphragm or feeder is more than 0.005 N / mg * cm <2>.

[2-3]

The laminated body as described in [2-1] or [2-2] whose said electric power feeder is a wire mesh, a metal nonwoven fabric, a punching metal, an expanded metal, or a foaming metal.

[2-4]

The laminated body in any one of [2-1]-[2-3] which has a layer which contains the mixture of the polymer into which the hydrophilic oxide particle and the ion exchange group were introduce | transduced as at least one surface layer of the said diaphragm.

[2-5]

The laminate according to any one of [2-1] to [2-4], in which a liquid is interposed between the electrolytic electrode and the diaphragm or the feeder.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve 3rd objective, the present inventors discovered that the said subject can be solved by the laminated body in which the diaphragm and the electrode for electrolysis are partially fixed, and completed this invention.

That is, this invention includes the following aspects.

[3-1]

Diaphragm,

Electrolytic electrode fixed to at least one area of the surface of the diaphragm

Has,

The laminated body whose ratio of the said area | region in the surface of the said diaphragm is more than 0% and less than 93%.

[3-2]

The electrode for electrolysis is Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb and Dy The laminated body as described in [3-1] containing the at least 1 sort (s) of catalyst component chosen from the group which consists of these.

[3-3]

The laminated body as described in [3-1] or [3-2] in which at least one part of the said electrode for electrolysis is fixed through the said diaphragm in the said area | region.

[3-4]

The laminate according to any one of [3-1] to [3-3], in which at least a part of the electrolytic electrode is positioned and fixed inside the diaphragm in the region.

[3-5]

The laminate according to any one of [3-1] to [3-4], further comprising a fixing member for fixing the diaphragm and the electrolytic electrode.

[3-6]

The laminated body as described in [3-5] in which at least one part of the said fixing member grips the said diaphragm and the said electrolytic electrode from the exterior.

[3-7]

The laminated body as described in [3-5] or [3-6] which at least one part of the said fixing member fixes the said diaphragm and the said electrolytic electrode by magnetic force.

(3-8)

The diaphragm comprises an ion exchange membrane containing an organic resin in a surface layer,

The laminated body in any one of [3-1]-[3-7] in which the said organic resin exists in the said area | region.

[3-9]

[3-1] to [3-8], wherein the diaphragm includes a first ion exchange resin layer and a second ion exchange resin layer having an EW different from the first ion exchange resin layer. The laminate described.

(3-10)

The said diaphragm is in any one of [3-1]-[3-8] which contains a 1st ion exchange resin layer and the 2nd ion exchange resin layer which has a functional group different from this 1st ion exchange resin layer. The laminate described.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve 4th objective, the present inventors solved the said subject by clamping at least one part of the laminated body of a diaphragm and an electrolytic electrode to an anode side gasket and a cathode side gasket. The present invention was completed by discovering.

That is, this invention includes the following aspects.

[4-1]

With the anode,

An anode frame supporting the anode;

An anode side gasket disposed on the anode frame;

A cathode facing the anode,

A cathode frame supporting the cathode;

A cathode side gasket disposed on the cathode frame and opposed to the anode side gasket;

A laminate comprising a diaphragm and an electrode for electrolysis, the laminate being disposed between the anode side gasket and the cathode side gasket.

And

At least a part of the laminate is sandwiched between the anode side gasket and the cathode side gasket,

The air flow resistance is 24 kPa · s when the electrolytic electrode is 50 mm × 50 mm in size, having a temperature of 24 ° C., a relative humidity of 32%, a piston speed of 0.2 cm / s, and an air flow of 0.4 cc / cm 2 / s. Electrolyzer less than / m.

[4-2]

The electrolytic cell as described in [4-1] whose thickness of the said electrode for electrolysis is 315 micrometers or less.

[4-3]

The electrolytic cell as described in [4-1] or [4-2] whose value which measured the said electrode for electrolysis by the following method (A) is 40 mm or less.

[4-method (A)]

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, a sample obtained by laminating an ion exchange membrane and the electrolytic electrode was wound and fixed on a curved surface of a vinyl chloride core material having an outer diameter of φ 32 mm, and left standing for 6 hours. Later, when the electrolytic electrode was separated and placed on a horizontal plate, the heights L ₁ and L ₂ in the vertical direction at both ends of the electrolytic electrode were measured, and these average values were measured.

(4-4)

The electrolytic cell according to any one of [4-1] to [4-3], wherein a mass per unit area of the electrode for electrolysis is 48 mg / cm 2 or less.

[4-5]

The electrolytic cell according to any one of [4-1] to [4-4], wherein a force applied per unit mass and unit area of the electrode for electrolysis is more than 0.005 N / mg · cm 2.

(4-6)

The electrolytic cell according to any one of [4-1] to [4-5], wherein the outermost peripheral edge of the laminate is located outside the current conduction surface direction than the outermost peripheral edges of the anode side gasket and the cathode side gasket.

(4-7)

The electrode for electrolysis is Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb and Dy The electrolyzer according to any one of [4-1] to [4-6], which contains at least one catalyst component selected from the group consisting of:

(4-8)

The electrolytic cell according to any one of [4-1] to [4-7], wherein at least a part of the electrolytic electrode is fixed through the diaphragm in the laminate.

(4-9)

The electrolytic cell according to any one of [4-1] to [4-7], wherein in the laminate, at least a part of the electrolytic electrode is positioned and fixed inside the diaphragm.

(4-10)

The electrolytic cell according to any one of [4-1] to [4-9], further comprising a fixing member for fixing the diaphragm and the electrolytic electrode in the laminate.

[4-11]

The electrolytic cell according to [4-10], wherein at least a part of the fixing member is fixed through the diaphragm and the electrolytic electrode in the laminate.

(4-12)

The electrolytic cell according to [4-10] or [4-11], wherein the fixing member includes a soluble material that is soluble in the electrolyte.

[4-13]

The electrolytic cell according to any one of [4-10] to [4-12], wherein at least a part of the fixing member holds the diaphragm and the electrolytic electrode externally in the laminate.

(4-14)

The electrolytic cell according to any one of [4-10] to [4-13], wherein at least a part of the fixing member is used to magnetically fix the diaphragm and the electrolytic electrode in the laminate.

(4-15)

The diaphragm comprises an ion exchange membrane containing an organic resin in a surface layer,

The electrolytic cell according to any one of [4-1] to [4-14], wherein the electrolytic electrode is fixed to the organic resin.

(4-16)

The said diaphragm is in any one of [4-1]-[4-15] containing a 1st ion exchange resin layer and the 2nd ion exchange resin layer which has an EW different from this 1st ion exchange resin layer. Described electrolyzer.

[4-17]

As the method for producing an electrolytic cell according to any one of [4-1] to [4-16],

A method for producing an electrolytic cell, comprising the step of sandwiching the laminate between the anode side gasket and the cathode side gasket.

(4-18)

As a method for updating a laminate in an electrolytic cell according to any one of [4-1] to [4-16],

Removing the laminate from the electrolytic cell by separating the laminate from the anode side gasket and the cathode side gasket;

Process of sandwiching the new laminate between the anode side gasket and the cathode side gasket

The update method of the laminated body which has this.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve 5th objective, the present inventors discovered that the said subject can be solved by using the winding object of the electrode for electrolysis or the said electrode for electrolysis, and a new diaphragm. The present invention has been completed.

That is, this invention includes the following aspects.

[5-1]

A new electrolytic cell is disposed in an existing electrolytic cell having a positive electrode, a negative electrode facing the positive electrode, and a diaphragm disposed between the positive electrode and the negative electrode. As a method for producing

The manufacturing method of the electrolytic cell using the said electrode for electrolysis or the winding body of the said laminated body.

[5-2]

The manufacturing method of the electrolytic cell as described in [5-1] which has the process (A) which hold | maintains the said electrode for electrolysis or the said laminated body in the wound state, and obtains the said wound body.

[5-3]

The manufacturing method of the electrolytic cell as described in [5-1] or [5-2] which has a process (B) which releases the wound state of the said winding body.

[5-4]

The manufacturing method of the electrolytic cell as described in [5-3] which has a process (C) which arrange | positions the said electrode for electrolysis or the said laminated body on at least one surface of the said anode and the said cathode after the said process (B).

[5-5]

As a method for updating an existing electrode by using an electrode for electrolysis,

The update method of the electrode using the winding body of the said electrode for electrolysis.

(5-6)

The update method of the electrode as described in [5-5] which has the process (A ') which hold | maintains the said electrode for electrolysis in a wound state, and obtains the said wound body.

[5-7]

The update method of the electrode as described in [5-5] or [5-6] which has the process (B ') of releasing the wound state of the said electrode for electrolysis.

(5-8)

The update method of the electrode as described in [5-7] which has a process (C ') which arrange | positions the said electrode for electrolysis on the surface of an existing electrode after the said process (B').

[5-9]

A method for manufacturing a wound body for updating an existing electrolytic cell having a positive electrode, a negative electrode facing the positive electrode, and a diaphragm disposed between the positive electrode and the negative electrode,

The manufacturing method of the winding body which has a process of winding the laminated body of an electrode for electrolysis or the said electrode for electrolysis, and a new diaphragm, and obtaining the said wound body.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve 6th objective, this inventor discovered that the said subject can be solved by integrating an electrolytic electrode and a new diaphragm under the temperature which the said diaphragm does not melt, and this invention Completed.

That is, this invention includes the following aspects.

[6-1]

A method for manufacturing a new electrolytic cell by disposing a laminate in an existing electrolytic cell having a positive electrode, a negative electrode facing the positive electrode, and a diaphragm disposed between the positive electrode and the negative electrode,

(A) obtaining the said laminated body by integrating an electrode for electrolysis and a new diaphragm under the temperature which the said diaphragm does not melt,

After the said process (A), the process (B) of exchanging the said diaphragm in an existing electrolytic cell with the said laminated body

Method for producing an electrolytic cell having a.

[6-2]

The method for producing an electrolytic cell according to [6-1], wherein the integration is performed under normal pressure.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve 7th objective, the present inventors discovered that the said subject could be solved by operation in an electrolytic cell frame, and completed this invention.

That is, this invention includes the following aspects.

(7-1)

An electrolytic electrode and a new diaphragm are provided in an existing electrolytic cell having a positive electrode, a negative electrode facing the positive electrode, a diaphragm fixed between the positive electrode and the negative electrode, and an electrolytic cell frame supporting the positive electrode, the negative electrode and the diaphragm. As a method for producing a new electrolytic cell by disposing a laminate containing,

A step (A) of releasing the fixing of the diaphragm in the electrolytic cell frame,

After the said process (A), the process (B) of exchanging the said diaphragm and said laminated body

Method for producing an electrolytic cell having a.

(7-2)

The process for producing an electrolytic cell according to [7-1], wherein the step (A) is performed by sliding the positive electrode and the negative electrode in the arrangement direction thereof, respectively.

(7-3)

The electrolytic cell manufacturing method as described in [7-1] or [7-2] which fixes the said laminated body in the said electrolytic cell frame by the press from the said positive electrode and the said negative electrode after the said process (B).

(7-4)

In the step (B), any one of [7-1] to [7-3], wherein the laminate is fixed on at least one surface of the positive electrode and the negative electrode under a temperature at which the laminate does not melt. Method for producing an electrolytic cell.

(7-5)

Disposing an electrolytic electrode in an existing electrolytic cell having an anode, a cathode facing the anode, a diaphragm fixed between the anode and the cathode, and an electrolytic cell frame supporting the anode, the cathode and the diaphragm. As a method for producing new electrolytic cells,

A step (A) of releasing the fixing of the diaphragm in the electrolytic cell frame,

After the step (A), the step (B ') of disposing the electrolytic electrode between the diaphragm and the anode or the cathode.

Method for producing an electrolytic cell having a.

(1) According to the electrode for electrolysis of the present invention, transportation and handling become easy, and the operation when starting a new electrolytic cell or updating a deteriorated electrode can be greatly simplified, and the electrolytic performance can also be maintained or improved. Can be.

(2) According to the laminate of the present invention, the work efficiency at the time of electrode update in an electrolytic cell can be improved, and also excellent electrolytic performance can be expressed after updating.

(3) According to the laminate of the present invention, from the viewpoint different from the above (2), the work efficiency at the time of electrode update in the electrolytic cell can be improved, and excellent electrolytic performance can be expressed even after the update.

(4) According to the electrolytic cell of this invention, while being excellent in electrolytic performance, damage of a diaphragm can be prevented.

(5) According to the manufacturing method of the electrolytic cell which concerns on this invention, the working efficiency at the time of electrode update in an electrolytic cell can be improved.

(6) According to the manufacturing method of the electrolytic cell which concerns on this invention, working efficiency at the time of electrode update in an electrolytic cell can be improved from a viewpoint different from said (5).

(7) According to the electrolytic cell manufacturing method which concerns on this invention, working efficiency at the time of electrode update in an electrolytic cell can be improved from a viewpoint different from said (5) and (6).

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing of the electrode for electrolysis which concerns on one Embodiment of this invention.
2 is a schematic cross-sectional view showing an embodiment of an ion exchange membrane.
3 is a schematic view for explaining the aperture ratio of the reinforcing core material constituting the ion exchange membrane.
It is a schematic diagram for demonstrating the method of forming the communication hole of an ion exchange membrane.
5 is a schematic cross-sectional view of an electrolytic cell.
6 is a schematic cross-sectional view showing a state in which two electrolytic cells are connected in series.
7 is a schematic diagram of an electrolytic cell.
8 is a schematic perspective view showing a step of assembling an electrolytic cell.
It is typical sectional drawing of the reverse current absorber with which an electrolysis cell is equipped.
It is a schematic diagram of the evaluation method of the force 1 applied per unit mass and unit area described in the Example.
It is a schematic diagram of the 280 mm diameter cylindrical winding evaluation method (1) described in the Example.
It is a schematic diagram of the diameter 280 mm cylindrical winding evaluation method (2) described in the Example.
It is a schematic diagram of the diameter 145 mm cylindrical winding evaluation method (3) described in the Example.
It is a schematic diagram of the elastic deformation test of the electrode as described in an Example.
It is a schematic diagram of the evaluation method of the softness after plastic deformation.
It is a schematic diagram of the electrode produced in the comparative example 13.
17 is a schematic view of a structure used for installing the electrode produced in Comparative Example 13 on a nickel mesh feeder.
It is a schematic diagram of the electrode produced in the comparative example 14.
19 is a schematic view of a structure used for installing the electrode produced in Comparative Example 14 on a nickel mesh feeder.
20 is a schematic view of the electrode produced in Comparative Example 15. FIG.
21 is a schematic view of a structure used for installing the electrode produced in Comparative Example 15 on a nickel mesh feeder.
It is typical sectional drawing of the electrode for electrolysis in one Embodiment of this invention.
It is a cross-sectional schematic diagram which shows one Embodiment of an ion exchange membrane.
It is a schematic diagram for demonstrating the opening ratio of the strengthening core material which comprises an ion exchange membrane.
It is a schematic diagram for demonstrating the method of forming the communication hole of an ion exchange membrane.
It is typical sectional drawing of an electrolysis cell.
27 is a schematic cross-sectional view showing a state in which two electrolytic cells are connected in series.
It is a schematic diagram of an electrolytic cell.
It is a typical perspective view which shows the process of assembling an electrolytic cell.
It is typical sectional drawing of the reverse current absorber with which an electrolysis cell is equipped.
It is a schematic diagram of the evaluation method of the force 1 applied per unit mass and unit area described in the Example.
It is a schematic diagram of the 280 mm diameter cylindrical winding evaluation method (1) described in the Example.
FIG. 33: is a schematic diagram of the diameter 280 mm cylindrical winding evaluation method (2) described in the Example.
It is a schematic diagram of the diameter 145 mm cylindrical winding evaluation method (3) described in the Example.
It is a schematic diagram of the elastic deformation test of the electrode as described in an Example.
It is a schematic diagram of the evaluation method of the softness after plastic deformation.
37 is a schematic view of the electrode produced in Example 34. FIG.
FIG. 38 is a schematic diagram of a structure used for installing the electrode prepared in Example 34 on a nickel mesh feeder. FIG.
39 is a schematic view of the electrode produced in Example 35. FIG.
40 is a schematic view of a structure used for installing the electrode prepared in Example 35 on a nickel mesh feeder.
41 is a schematic view of the electrode produced in Example 36. FIG.
FIG. 42 is a schematic diagram of a structure used for installing the electrode prepared in Example 36 on a nickel mesh feeder. FIG.
It is typical sectional drawing of the electrode for electrolysis in one Embodiment of this invention.
44 is a schematic sectional view illustrating one embodiment of the ion exchange membrane.
It is a schematic diagram for demonstrating the aperture ratio of the strengthening core material which comprises an ion exchange membrane.
It is a schematic diagram for demonstrating the method of forming the communication hole of an ion exchange membrane.
It is typical sectional drawing of the laminated body which illustrates the aspect in which at least one part of the electrode for electrolysis is fixed through a septum. FIG. 47B is an explanatory diagram showing a step for obtaining the structure of FIG. 47A. FIG.
It is typical sectional drawing of the laminated body which illustrates the aspect in which at least one part of the electrode for electrolysis is located inside and fixed to a diaphragm. 48B is an explanatory diagram showing a step for obtaining the structure of FIG. 48A.
49A to 49C are schematic cross-sectional views of a laminate illustrating an aspect of fixing using a thread-shaped fixing member as a fixing member for fixing the diaphragm and the electrolytic electrode.
It is a schematic cross section of the laminated body which shows the aspect which fixes using a organic resin as a fixing member for fixing a diaphragm and an electrode for electrolysis.
51A is a schematic sectional view of a laminate illustrating an embodiment in which at least a part of the fixing member grips and fixes the diaphragm and the electrolytic electrode from the outside. It is typical sectional drawing of the laminated body which shows the aspect which at least one part of the fixing member fixes a diaphragm and an electrolytic electrode by magnetic force.
It is typical sectional drawing of an electrolysis cell.
53 is a schematic cross-sectional view showing a state in which two electrolytic cells are connected in series.
It is a schematic diagram of an electrolytic cell.
55 is a schematic perspective view illustrating a step of assembling an electrolytic cell.
56 is a schematic cross-sectional view of a reverse current absorber that an electrolytic cell can have.
57 is an explanatory diagram showing a laminate in Example 1. FIG.
58 is an explanatory diagram showing a laminate in Example 2. FIG.
59 is an explanatory diagram showing a laminate in Example 3. FIG.
60 is an explanatory diagram showing a laminate in Example 4. FIG.
FIG. 61 is an explanatory diagram showing a laminate in Example 5. FIG.
FIG. 62 is an explanatory diagram showing a laminate in Example 6. FIG.
63 is a schematic sectional view of an electrolysis cell.
64A is a schematic cross-sectional view showing a state in which two electrolytic cells in a conventional electrolytic cell are connected in series. 64B is a schematic cross-sectional view showing a state in which two electrolytic cells are connected in series in the electrolytic cell of this embodiment.
Fig. 65 is a schematic diagram of the electrolytic cell.
66 is a schematic perspective view showing a step of assembling an electrolytic cell.
67 is a schematic sectional view of a reverse current absorber that an electrolytic cell can have.
It is typical sectional drawing of the electrode for electrolysis in one Embodiment of this invention.
69 is a schematic sectional view illustrating one embodiment of the ion exchange membrane.
It is a schematic diagram for demonstrating the opening ratio of the strengthening core material which comprises an ion exchange membrane.
It is a schematic diagram for demonstrating the method of forming the communication hole of an ion exchange membrane.
It is explanatory drawing for demonstrating the positional relationship of a laminated body and a gasket.
It is explanatory drawing for demonstrating the positional relationship of a laminated body and a gasket.
FIG. 74A is a schematic cross-sectional view of a laminate illustrating an embodiment in which at least a part of an electrode for electrolysis is fixed through a septum. 74B is an explanatory diagram showing a step for obtaining the structure in FIG. 74A.
FIG. 75A is a schematic cross-sectional view of a laminate illustrating an embodiment in which at least a part of the electrolytic electrode is positioned and fixed inside the diaphragm. FIG. FIG. 75B is an explanatory diagram showing a step for obtaining the structure of FIG. 75A.
76A-76C are typical sectional drawing of the laminated body which shows the aspect which fixes using a thread-shaped fixing member as a fixing member for fixing a diaphragm and an electrolytic electrode.
77 is a schematic sectional view of a laminate illustrating an aspect of fixing using an organic resin as a fixing member for fixing the diaphragm and the electrode for electrolysis.
78A is a schematic sectional view of a laminate illustrating an embodiment in which at least a part of the fixing member grips and fixes the diaphragm and the electrolytic electrode from the outside. 78B is a schematic sectional view of a laminate illustrating an embodiment in which at least a part of the fixing member fixes the diaphragm and the electrode for electrolysis by magnetic force.
79 is a schematic view of the evaluation method of the force 1 applied per unit mass and unit area described in Examples.
FIG. 80: is a schematic diagram of the diameter 280 mm cylindrical winding evaluation method (1) described in the Example.
FIG. 81: is a schematic diagram of the 280 mm diameter cylinder winding evaluation method (2) described in the Example.
FIG. 82: is a schematic diagram of the diameter 145 mm cylindrical winding evaluation method (3) described in the Example.
It is a schematic diagram of the flexibility evaluation of the electrode as described in an Example.
It is a schematic diagram of the evaluation method of the softness after plastic deformation.
85 is a schematic view of the electrode produced in Example 35. FIG.
86 is a schematic diagram of a structure used for installing the electrode prepared in Example 35 on a nickel mesh feeder.
87 is a schematic view of the electrode produced in Example 36. FIG.
88 is a schematic diagram of a structure used for installing the electrode produced in Example 36 on a nickel mesh feeder.
89 is a schematic view of the electrode produced in Example 37. FIG.
90 is a schematic view of a structure used for installing the electrode prepared in Example 37 on a nickel mesh feeder.
91 is a schematic sectional view of an electrolysis cell.
FIG. 92 is a schematic sectional view illustrating a state in which two electrolytic cells are connected in series.
93 is a schematic diagram of the electrolytic cell.
94 is a schematic perspective view showing a step of assembling an electrolytic cell.
95 is a schematic sectional view of a reverse current absorber that an electrolytic cell may have.
96 is a schematic sectional view of an electrode for electrolysis in one embodiment of the present invention.
97 is a schematic sectional view illustrating one embodiment of the ion exchange membrane.
It is a schematic diagram for demonstrating the opening ratio of the strengthening core material which comprises an ion exchange membrane.
It is a schematic diagram for demonstrating the method of forming the communication hole of an ion exchange membrane.
100 is a schematic view of the laminate prepared in Example 1. FIG.
It is a schematic diagram at the time of winding the laminated body created in Example 1 and creating a wound body.
It is a schematic diagram of the laminated body created in Example 4. FIG.
103 is a schematic sectional view of an electrolytic cell.
FIG. 104 is a schematic cross-sectional view showing a state in which two electrolytic cells are connected in series.
105 is a schematic diagram of an electrolytic cell.
106 is a schematic perspective view illustrating a step of assembling an electrolytic cell.
107 is a schematic sectional view of a reverse current absorber that an electrolytic cell can have.
108 is a schematic sectional view of an electrode for electrolysis in one embodiment of the present invention.
It is a cross-sectional schematic diagram which illustrates one Embodiment of an ion exchange membrane.
It is a schematic diagram for demonstrating the opening ratio of the strengthening core material which comprises an ion exchange membrane.
It is a schematic diagram for demonstrating the method of forming the communication hole of an ion exchange membrane.
112 is a schematic sectional view of an electrolytic cell.
113 is a schematic sectional view showing a state in which two electrolytic cells are connected in series.
114 is a schematic view of an electrolytic cell.
115 is a schematic perspective view illustrating a step of assembling an electrolytic cell.
116 is a schematic sectional view of a reverse current absorber that an electrolytic cell can have.
117a is a schematic diagram of an electrolytic cell for illustrating an example of each step according to the first aspect of the present embodiment. 117b is a schematic perspective view corresponding to FIG. 117a.
118a is a schematic diagram of an electrolytic cell for explaining an example of each step according to the second aspect of the present embodiment. FIG. 118B is a schematic perspective view corresponding to FIG. 118A.
119 is a schematic sectional view of the electrode for electrolysis in one embodiment of the present invention.
120 is a schematic sectional view illustrating one embodiment of the ion exchange membrane.
It is a schematic diagram for demonstrating the opening ratio of the strengthening core material which comprises an ion exchange membrane.
It is a schematic diagram for demonstrating the method of forming the communication hole of an ion exchange membrane.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention (henceforth also called this embodiment) is demonstrated in detail, referring drawings as needed for every <1st embodiment>-<7th embodiment>. The following embodiment is an illustration for demonstrating this invention, and this invention is not limited to the following content. In addition, an accompanying drawing shows an example of embodiment, and a form is not limited to this and is not interpreted. This invention can be suitably modified and implemented within the range of the summary. In addition, unless otherwise indicated, positional relationship, such as up, down, left, and right, in a figure is based on the positional relationship shown in a figure. The dimensions and ratios of the drawings are not limited to those shown.

First Embodiment

Here, the first embodiment of the present invention will be described in detail with reference to Figs.

[Electrode Electrode]

Electrolytic electrodes of the first embodiment (hereinafter, simply referred to as "the present embodiment" in the section of <first embodiment>) can obtain good handling properties, and are capable of obtaining a deteriorated membrane such as an ion exchange membrane or a microporous membrane, and deterioration. It has good adhesion with an electrode, an uncoated feeder, and the like, and from the viewpoint of economics, the mass per unit area is 48 mg / cm 2 or less. Moreover, it is preferable that it is 30 mg / cm <2> or less in this point, More preferably, it is 20 mg / cm <2> or less and 15 mg / cm <2> or less from a comprehensive viewpoint which combined handling property, adhesiveness, and economics. Although a lower limit is not specifically limited, For example, it is about 1 mg / cm <2>.

The said mass per unit area can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, etc., for example. More specifically, for example, if the thickness is the same, the mass per unit area tends to be smaller when the porosity is increased, and the mass per unit area tends to be larger when the porosity is reduced.

The electrode for electrolysis of this embodiment can obtain favorable handling property, and has a favorable adhesive force with a diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode, an uncoated feeder, etc., per unit mass / unit area. The force applied is at least 0.08 N / (mg · cm 2). In addition, it is preferably 0.1 N / (mg · cm 2) or more, more preferably 0.14 N / (mg · cm 2) or more, and still more preferably a large size (eg, size 1.5 m × 2.5 m). It is 0.2 N / (mg * cm <2>) or more from a viewpoint of the handling becoming easier. Although an upper limit is not specifically limited, It is preferable that it is 1.6 N / (mg * cm <2>) or less, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred.

If the electrode for electrolysis of this embodiment is an electrode with a large elastic deformation area, better handling property can be obtained, and it will provide better adhesive force, such as a diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode, an uncoated feeder, etc. From the viewpoint of having, the thickness of the electrolytic electrode is preferably 315 µm or less, more preferably 220 µm or less, still more preferably 170 µm or less, even more preferably 150 µm or less, and particularly preferably 145 µm or less. 140 micrometers or less are more preferable, 138 micrometers or less are further more preferable, and 135 micrometers or less are further more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, from a viewpoint similar to the above, 130 micrometers or less are preferable, less than 130 micrometers are more preferable, 115 micrometers or less are more preferable, and 65 micrometers or less are still more preferable. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, in this embodiment, a "elastic deformation area | region is wide" means that it is difficult to produce the curvature resulting from winding after winding an electrode for electrolysis to make a winding body, and canceling a wound state. In addition, the thickness of an electrode for electrolysis means the thickness which combined the electrode base material for electrolysis and a catalyst layer, when including the catalyst layer mentioned later.

According to the electrode for electrolysis of this embodiment, as mentioned above, it has a favorable adhesive force, such as a diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode, a catalyst uncoated feeder, etc., and integrates it with a diaphragm, such as an ion exchange membrane and a microporous membrane, It is available. Therefore, when updating an electrode, an electrode can be updated by simple operation | movement, such as an update of a diaphragm, without carrying out complicated replacement work, such as peeling an electrode fixed to an electrolysis cell, and therefore working efficiency improves significantly. do. In addition, even when only a feeder is provided in a new electrolytic cell (that is, when an electrode without a catalyst layer is provided), the electrolytic electrode of the present embodiment can act as an electrode only by sticking to the feeder. As a result, it is possible to significantly reduce or zero the catalyst coating.

Moreover, according to the electrode for electrolysis of this embodiment, electrolytic performance can be made to be equivalent to or improved in the case of a new article.

The electrolytic electrode of the present embodiment can be stored, transported to a customer, etc. in a state of being wound in a pipe made of vinyl chloride or the like (roll type or the like), for example, and handling is greatly facilitated.

The force applied can be measured by the following method (i) or (ii) and is as having described in the Example in detail. The force applied is the value obtained by the measurement of the method (i) (also called "the applied force 1") and the value obtained by the measurement of the method (ii) (also called the "the applied force 2"). Although this may be same or different, any value becomes 0.08 N / (mg * cm <2>) or more.

The said applied force can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, arithmetic mean surface roughness, etc., for example. More specifically, for example, when the porosity is increased, the applied force tends to be small, and when the porosity is decreased, the applied force tends to be large.

[Method (i)]

Nickel plate obtained by blasting with alumina of particle number 320 (thickness 1.2 mm, width 200 mm) and an ion exchange membrane coated with inorganic particles and a binder on both sides of a membrane of a perfluorocarbon polymer into which an ion exchanger was introduced (horizontal 170 mm in length and the details of the ion-exchange membrane here, as described in the Example) and the electrode sample for electrolysis (130 mm in length) were laminated in this order, and this laminate was sufficiently immersed in pure water, A sample for measurement is obtained by removing excess moisture adhering to the laminate surface. In addition, the arithmetic mean surface roughness Ra of the nickel plate after a blasting process is 0.7 micrometer. The specific calculation method of arithmetic mean surface roughness Ra is as having described in the Example.

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrolytic electrode samples in this measurement sample were raised to 10 mm / min in the vertical direction using a tensile compression tester, so that the electrolytic electrode samples were in the vertical direction. Measure the weight when it rises by 10 mm. This measurement is performed three times to calculate an average value.

The average value is divided by the area of the overlapping portion of the electrolytic electrode sample and the ion exchange membrane and the mass of the electrode sample for electrolysis of the portion overlapping the ion exchange membrane, and the force applied per unit mass and unit area (1) (N / mg · cm 2) is calculated.

The force (1) applied per unit mass and unit area obtained by the method (i) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is 0.08 N / (mg * cm <2>) or more from the viewpoint of having a thing, Preferably it is 0.1 N / (mg * cm <2>) or more, More preferably, handling in a large size (for example, size 1.5 m x 2.5 m) It is 0.2 N / (mg * cm <2>) or more from a viewpoint of this further becoming easier. Although an upper limit is not specifically limited, It is preferable that it is 1.6 N / (mg * cm <2>) or less, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred.

When the electrode for electrolysis of this embodiment satisfies the force 1 applied, since it can be used integrally with diaphragms, such as an ion exchange membrane and a microporous membrane, when an electrode is updated, it is made to the electrolysis cell by methods, such as welding. The replacement work of the fixed cathode and the anode becomes unnecessary, and the work efficiency is greatly improved. In addition, by using the electrolytic electrode of this embodiment as an electrode integrated with an ion exchange membrane, electrolytic performance can be made equivalent to or improved in the case of a new article.

When shipping a new electrolytic cell, the catalyst coating was conventionally coated on the electrode fixed to the electrolytic cell, but since it can be used as an electrode only by combining the electrolytic electrode of this embodiment with the electrode which does not have a catalyst coating, catalyst coating It is possible to greatly reduce or zero the amount of the production process and the catalyst to achieve this. The conventional electrode, in which the catalyst coating is significantly reduced or zero, can be electrically connected to the electrode for electrolysis of the present embodiment and function as a feeder for flowing a current.

[Method (ii)]

A nickel plate obtained by blasting with alumina of particle number 320 (thickness 1.2 mm, width 200 mm, same nickel plate as the above method (i)) and an electrolytic electrode sample (width 130 mm) were laminated in this order. After fully immersing this laminated body with pure water, the sample for a measurement is obtained by removing the excess moisture adhering to the laminated body surface. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples for electrolysis in this measurement sample were raised to 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples for electrolysis were vertical. The weight at the time of 10 mm rise in the direction is measured. This measurement is performed three times to calculate an average value.

This average value is divided by the area of the overlapping portion of the electrolytic electrode sample and the nickel plate and the mass of the electrolytic electrode sample at the portion overlapping the nickel plate, and the adhesive force (2) per unit mass and unit area (N / mg Cm 2) is calculated.

The force (2) applied per unit mass and unit area obtained by the method (ii) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is 0.08 N / (mg * cm <2>) or more from the viewpoint of having a thing, Preferably it is 0.1 N / (mg * cm <2>) or more, More preferably, handling in a large size (for example, size 1.5 m x 2.5 m) It is 0.14 N / (mg * cm <2>) or more from a viewpoint that this becomes further easier. Although an upper limit is not specifically limited, It is preferable that it is 1.6 N / (mg * cm <2>) or less, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred.

When the force 2 applied by the electrode for electrolysis of this embodiment is satisfied, it can be stored, transported to a customer, etc. in the state wound (for example, roll type) wound on the pipe made from vinyl chloride, etc., and handling becomes large. It becomes easy. In addition, by adhering the electrode for electrolysis of this embodiment to the deteriorated electrode, electrolytic performance can be made to be equivalent to or improved in the case of a new article.

In this embodiment, the liquid which exists between a diaphragm, such as an ion exchange membrane and a microporous membrane, and an electrolytic electrode or an electric power feeder (deteriorated electrode or uncatalyzed electrode), and an electrolytic electrode has surface tension, such as water and an organic solvent. Any liquid may be used as long as it generates. The greater the surface tension of the liquid, the greater the force exerted between the diaphragm and the electrode for electrolysis or between the metal plate and the electrode for electrolysis. Therefore, a liquid having a high surface tension is preferable. Examples of the liquid include the following (the numerical values in parentheses indicate the surface tension of the liquid).

Hexane (20.44 mN / m), Acetone (23.30 mN / m), Methanol (24.00 mN / m), Ethanol (24.05 mN / m), Ethylene glycol (50.21 mN / m), Water (72.76 mN / m)

If the liquid has a high surface tension, the diaphragm and the electrode for electrolysis, or the metal porous plate or metal plate (feeder), and the electrode for electrolysis are integrated (to be laminated), so that the electrode can be easily updated. The liquid between the diaphragm and the electrode for electrolysis, or the metal porous plate or the metal plate (feeder), and the electrode for electrolysis should be such that the amount of adhesion is due to the surface tension. Even if it is mixed with the electrolyte after being installed in, it does not affect the electrolysis itself.

From a practical point of view, it is preferable to use the liquid whose surface tensions, such as ethanol, ethylene glycol, water, are 20 mN / m-80 mN / m. In particular, an aqueous solution obtained by dissolving caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like in water or alkali is preferable. It is also possible to adjust the surface tension by including surfactants in such liquids. By including surfactant, the adhesiveness of a diaphragm and an electrode for electrolysis, or a metal plate, and an electrode for electrolysis changes, and handling property can be adjusted. There is no restriction | limiting in particular as surfactant, Both an ionic surfactant and a nonionic surfactant can be used.

It is preferable that the electrolytic electrode of this embodiment contains an electrolytic electrode base material and a catalyst layer. Although the thickness (gauge thickness) of the said electrode base for electrolysis is not specifically limited, favorable handling property can be obtained, and it has favorable adhesive force with a diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode, and a catalyst uncoated feeder, 300 micrometers or less are preferable, and 205 micrometers or less are more preferable from a viewpoint that it can be rolled up suitably and can bend favorably and the handling in a large size (for example, size 1.5m * 2.5m) becomes easy, 155 micrometers or less are further more preferable, 135 micrometers or less are more preferable, 125 micrometers or less are still more preferable, 120 micrometers or less are still more preferable, 100 micrometers or less are much more preferable, From a handling and economical viewpoint, 50 micrometers or less are further more preferable. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

Although the electrode for electrolysis of this embodiment is not specifically limited, From a viewpoint that a favorable handling property can be obtained and it has favorable adhesive force with a diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode, and a catalyst uncoated feeder, It is preferable that the ratio measured by the following method (2) is 90% or more, It is more preferable that it is 92% or more, and from a viewpoint that handling in a large size (for example, size 1.5 m x 2.5 m) becomes easy. More preferably, 95% or more. The upper limit is 100%.

[Method (2)]

An ion exchange membrane (170 mm wide) and an electrolytic electrode sample (130 mm wide) are laminated in this order. Under a condition of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 280 mm) so that the electrode sample for electrolysis in the laminate is the outer side, and the laminate and the pipe are placed. Soaked sufficiently with pure water, the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio of the area of the portion where the ion exchange membrane (170 mm long) and the electrode sample for electrolysis are in close contact with each other (%) Measure

Although the electrode for electrolysis of this embodiment is not specifically limited, Good handling property can be obtained, It has a favorable adhesive force with the diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode, and a catalyst uncoated feeder, and is suitable for a roll type. It is preferable that the ratio measured by the following method (3) is 75% or more, It is more preferable that it is 80% or more, and also a large size (for example, size 1.5 m x) from a viewpoint that it can wind and bend favorably. It is more preferable that it is 90% or more from a viewpoint that the handling in 2.5 m) becomes easy. The upper limit is 100%.

[Method (3)]

An ion exchange membrane (170 mm wide) and an electrolytic electrode sample (130 mm wide) are laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 145 mm) so that the electrode sample for electrolysis in the laminate is the outer side, and the laminate and the pipe are placed. Soaked sufficiently with pure water, the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio of the area of the portion where the ion exchange membrane (170 mm long) and the electrode sample for electrolysis are in close contact with each other (%) Measure

Although the electrode for electrolysis of this embodiment is not specifically limited, Good handling property can be obtained, it has good adhesive force with the diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode, and a catalyst uncoated feeder, and it generate | occur | produces during electrolysis It is preferable that it is a porous structure from a viewpoint of the retention prevention of the said gas, and the porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80% or less, still more preferably 20 to 75%.

In addition, an opening ratio is a ratio of an opening part per unit volume. The calculation method varies depending on whether the opening is also considered to submicron order or only the visible opening. In this embodiment, the volume V was calculated from the values of the gauge thickness, the width, and the length of the electrode, and the weight W was measured, and the porosity A was calculated by the following formula.

A = (1- (W / (V × ρ)) × 100

ρ is the density (g / cm 3) of the material of the electrode. For example, 8.908 g / cm 3 for nickel and 4.506 g / cm 3 for titanium. The adjustment of the porosity is to change the area punching the metal per unit area if the punching metal, change the SW (short diameter), LW (long diameter), the feeding value if the expanded metal, the mesh diameter of the metal fiber, By changing the number of meshes, changing the pattern of the photoresist to be used for electroforming, changing the metal fiber diameter and fiber density for nonwoven fabrics, and changing the mold for forming the voids for the foamed metal, etc. Adjust

As for the electrode for electrolysis in this embodiment, it is preferable that the value measured by the following method (A) is 40 mm or less from a viewpoint of handling property, More preferably, it is 29 mm or less, More preferably, it is 10 mm It is below, More preferably, it is 6.5 mm or less. In addition, the specific measuring method is as having described in the Example.

[Method (A)]

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, a sample obtained by laminating an ion exchange membrane and the electrolytic electrode was wound and fixed on a curved surface of a vinyl chloride core material having an outer diameter of φ 32 mm, and left standing for 6 hours. Later, when the electrolytic electrode was separated and placed on a horizontal plate, the heights L ₁ and L ₂ in the vertical direction at both ends of the electrolytic electrode were measured, and these average values were measured.

The electrolytic electrode in this embodiment makes the electrolytic electrode 50 mm x 50 mm in size, and has a temperature of 24 degreeC, a relative humidity of 32%, a piston speed of 0.2 cm / s, and an airflow of 0.4 cc / cm <2> / s. In one case (hereinafter, also referred to as "measurement condition 1"), the ventilation resistance (hereinafter also referred to as "airflow resistance 1") is preferably 24 kPa · s / m or less. High ventilation resistance means that air is difficult to flow, and indicates a high density. In this state, since the product by electrolysis stays in the electrode and the reaction substrate becomes difficult to diffuse into the electrode, the electrolytic performance (voltage, etc.) tends to be deteriorated. In addition, the concentration of the film surface tends to increase. Specifically, the caustic concentration tends to increase on the cathode side, and the supplyability of brine tends to decrease on the anode side. As a result, the product remains at a high concentration at the interface where the membrane and the electrode contact, leading to damage of the membrane, leading to voltage rise and film damage on the cathode surface and film damage on the anode surface. In this embodiment, in order to prevent such a problem, it is preferable to make a ventilation resistance 24 kPa * s / m or less. It is more preferable that it is less than 0.19 kPa * s / m from a viewpoint similar to the above, It is still more preferable that it is 0.15 kPa * s / m or less, It is still more preferable that it is 0.07 kPa * s / m or less.

In addition, in this embodiment, when the ventilation resistance is greater than or equal to a certain level, in the case of the negative electrode, NaOH generated at the electrode tends to remain at the interface between the electrode and the diaphragm, resulting in a high concentration. In order to prevent the damage to the diaphragm which may occur due to such retention, it is preferably less than 0.19 kPa · s / m, more preferably 0.15 kPa · s / m or less. And it is more preferable that it is 0.07 kPa * s / m or less.

On the other hand, when the airflow resistance is low, the area of the electrode is small, so that the electrolytic area is small and the electrolytic performance (voltage, etc.) tends to be deteriorated. When the ventilation resistance is zero, since the electrode for electrolysis is not provided, a power supply functions as an electrode and there exists a tendency for electrolytic performance (voltage etc.) to deteriorate remarkably. In this regard, the lower limit specified as the ventilation resistance 1 is not particularly limited, but is preferably more than 0 kPa · s / m, more preferably 0.0001 kPa · s / m or more, still more preferably 0.001 kPa S / m or more.

In addition, the ventilation resistance 1 may not be able to obtain sufficient measurement accuracy in 0.07 kPa * s / m or less on the measuring method. In view of this, for the electrode for electrolysis having a ventilation resistance 1 of 0.07 kPa · s / m or less, the ventilation resistance according to the following measuring method (hereinafter also referred to as “measurement condition 2”) (hereinafter also referred to as “airflow resistance 2”) Evaluation by is also possible. That is, the ventilation resistance 2 sets the electrode for electrolysis to the size of 50 mm x 50 mm, and it is the ventilation | emission when the temperature is 24 degreeC, the relative humidity 32%, the piston speed 2 cm / s, and the ventilation amount 4 cc / cm <2> / s. Resistance.

The measuring method of specific ventilation resistance 1 and 2 is as having described in the Example.

The ventilation resistances 1 and 2 can be in the above ranges by appropriately adjusting the porosity, electrode thickness, and the like described later, for example. More specifically, for example, when the pore rate is increased, the airflow resistances 1 and 2 tend to be small, and when the porosity is small, the airflow resistances 1 and 2 tend to be large.

EMBODIMENT OF THE INVENTION Hereinafter, one form of the electrode for electrolysis of this embodiment is demonstrated.

It is preferable that the electrolytic electrode which concerns on this embodiment contains an electrolytic electrode base material and a catalyst layer. The catalyst layer may be composed of a plurality of layers as described below or may have a single layer structure.

As shown in FIG. 1, the electrolytic electrode 100 according to the present embodiment includes a pair of first layers 20 covering both surfaces of the electrolytic electrode substrate 10 and the electrolytic electrode substrate 10. It is provided. It is preferable that the 1st layer 20 coat | covers the electrolytic electrode base material 10 whole. As a result, the catalytic activity and durability of the electrode tend to be improved. In addition, the first layer 20 may be laminated only on one surface of the electrode base 10 for electrolysis.

In addition, as shown in FIG. 1, the surface of the first layer 20 may be covered with the second layer 30. It is preferable that the 2nd layer 30 coat | covers the 1st whole layer 20. In addition, only one surface of the first layer 20 may be laminated on the second layer 30.

(Electrode base for electrolysis)

Although it does not specifically limit as the electrode base material 10 for electrolysis, For example, the valve metal represented by nickel, a nickel alloy, stainless steel, titanium, etc. can be used. It is preferable to include at least one element selected from nickel (Ni) and titanium (Ti). That is, it is preferable that an electrolytic electrode base material contains at least 1 sort (s) of element chosen from nickel (Ni) and titanium (Ti).

When stainless steel is used in a high concentration aqueous alkali solution, considering that iron and chromium are eluted, and that the electrical conductivity of stainless steel is about 1/10 of nickel, the electrolytic electrode substrate includes nickel (Ni). The substrate is preferred.

In addition, when the electrolytic electrode base material 10 is used in the chlorine gas generation | occurence atmosphere in the high concentration saline solution near saturation, it is preferable that a material is titanium with high corrosion resistance.

There is no restriction | limiting in particular in the shape of the electrode base material 10 for electrolysis, An appropriate shape can be selected according to the objective. As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used. Especially, a punching metal or an expanded metal is preferable. In addition, electroforming is a technique which manufactures a metal thin film of a precise pattern by combining photolithography and an electroplating method. It is a method of pattern-forming with a photoresist on a board | substrate, electroplating to the part which is not protected by a resist, and obtaining metal foil.

The shape of the electrode base material for electrolysis has suitable specifications depending on the distance between the anode and the cathode in the electrolytic cell. Although not particularly limited, in the case where the anode and the cathode have a finite distance, an expanded metal or a punched metal shape can be used, and in the case of a so-called zero gap electrolytic cell in which the ion exchange membrane and the electrode are in contact, a woven mesh woven with fine wires , Foamed metal, metal nonwoven fabric, expanded metal, punched metal, metal porous foil and the like can be used.

Examples of the electrode base 10 for electrolysis include metal foil, wire mesh, metal nonwoven fabric, punched metal, expanded metal or expanded metal.

As a board | plate material before processing with a punching metal and an expanded metal, the board | plate material roll-molded, electrolytic foil, etc. are preferable. It is preferable that an electrolytic foil is further plated with the same element as a base material as a post-process, and to form an unevenness | corrugation on the surface.

Moreover, as mentioned above, the thickness of the electrolytic electrode base material 10 is preferably 300 µm or less, more preferably 205 µm or less, still more preferably 155 µm or less, even more preferably 135 µm or less, It is still more preferable that it is 125 micrometers or less, It is still more preferable that it is 120 micrometers or less, It is still more preferable that it is 100 micrometers or less, It is further more preferable that it is 50 micrometers or less from a viewpoint of handling property and economical efficiency. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In the electrode base for electrolysis, it is preferable to relieve the residual stress at the time of processing by annealing the electrode base for electrolysis in an oxidizing atmosphere. Moreover, in order to improve the adhesiveness with the catalyst layer coat | covered on the said surface, the surface of an electrolytic electrode base material is used to form an unevenness | corrugation using a steel grid, an alumina grid, etc., and to increase a surface area by acid treatment after that. Do. It is preferable to perform plating treatment with the same element as the substrate and to increase the surface area.

In order to make the surface of the 1st layer 20 and the electrode base material 10 for electrolysis adhere to the electrode base material 10 for electrolysis, it is preferable to perform the process which increases a surface area. Examples of the treatment for increasing the surface area include a blast treatment using a cut wire, a steel grid, an alumina grid, and the like, an acid treatment using sulfuric acid or hydrochloric acid, a plating treatment using the same element as the substrate, and the like. Although arithmetic mean surface roughness Ra of the surface of a base material is not specifically limited, 0.05 micrometer-50 micrometers are preferable, 0.1-10 micrometers is more preferable, 0.1-5 micrometers is still more preferable.

Next, the case where the electrode for electrolysis of this embodiment is used as a salt electrolytic anode is demonstrated.

(1st floor)

In FIG. 1, the 1st layer 20 which is a catalyst layer contains at least 1 sort (s) of oxide of ruthenium oxide, iridium oxide, and titanium oxide. Of ruthenium oxide RuO _2, etc., it may be mentioned. IrO ₂ etc. are mentioned as an iridium oxide. Examples of titanium oxides include TiO ₂ . The first layer 20 preferably contains two kinds of oxides of ruthenium oxide and titanium oxide, or three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide. Thereby, the 1st layer 20 becomes a more stable layer, and also adhesiveness with the 2nd layer 30 improves more.

In the case where the first layer 20 includes two kinds of oxides of ruthenium oxide and titanium oxide, titanium contained in the first layer 20 with respect to one mole of ruthenium oxide included in the first layer 20. It is preferable that it is 1-9 mol, and, as for an oxide, it is more preferable that it is 1-4 mol. By setting the composition ratio of the two kinds of oxides in this range, the electrolytic electrode 100 exhibits excellent durability.

When the first layer 20 includes three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide, the first layer 20 is included in the first layer 20 with respect to one mole of ruthenium oxide contained in the first layer 20. It is preferable that it is 0.2-3 mol, and, as for the iridium oxide used, it is more preferable that it is 0.3-2.5 mol. Moreover, it is preferable that it is 0.3-8 mol, and, as for 1 mol of titanium oxide contained in the 1st layer 20 with respect to 1 mol of ruthenium oxide contained in the 1st layer 20, it is more preferable. By making the composition ratio of three types of oxides into this range, the electrode 100 for electrolysis shows the outstanding durability.

When the 1st layer 20 contains at least 2 types of oxide chosen from a ruthenium oxide, an iridium oxide, and a titanium oxide, it is preferable that these oxides form a solid solution. By forming the oxide solid solution, the electrolytic electrode 100 exhibits excellent durability.

In addition to the above composition, as long as it contains at least one oxide of ruthenium oxide, iridium oxide and titanium oxide, those having various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like, referred to as DSA (registered trademark), may be used as the first layer 20.

The first layer 20 does not need to be a single layer, but may include a plurality of layers. For example, the first layer 20 may include a layer containing three kinds of oxides and a layer containing two kinds of oxides. 0.05-10 micrometers is preferable and, as for the thickness of the 1st layer 20, 0.1-8 micrometers is more preferable.

(2nd floor)

It is preferable that the 2nd layer 30 contains ruthenium and titanium. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

It is preferable that the 2nd layer 30 contains palladium oxide, the solid solution of palladium oxide, and platinum, or the alloy of palladium and platinum. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

The longer the longer the thickness of the second layer 30 can maintain the electrolytic performance, the thickness of the second layer 30 is preferably 0.05 to 3 m.

Next, the case where the electrode for electrolysis of this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

As a component of the first layer 20 which is a catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal include at least one kind, the alloy containing the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide and the platinum group metal is platinum, palladium, rhodium, It is preferable to contain at least 1 type of platinum group metal among ruthenium and iridium.

As a platinum group metal, it is preferable to contain platinum.

It is preferable that a platinum group metal oxide contains ruthenium oxide.

It is preferable that a platinum group metal hydroxide contains a ruthenium hydroxide.

As a platinum group metal alloy, it is preferable to include the alloy of platinum, nickel, iron, and cobalt.

Moreover, it is preferable to contain the oxide or hydroxide of a lanthanoid element as a 2nd component as needed. As a result, the electrolytic electrode 100 exhibits excellent durability.

The oxide or hydroxide of the lanthanoid-based element preferably contains at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium.

Moreover, it is preferable to contain the oxide or hydroxide of a transition metal as a 3rd component as needed.

By adding the third component, the electrolytic electrode 100 exhibits more excellent durability and can reduce the electrolytic voltage.

Examples of preferred combinations include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + platinum + palladium Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium + Sulfur, Ruthenium + Lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + samarium + cobalt, ruthenium + samarium + gallium, ruthenium + samarium + gallium, ruthenium + Samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + Nickel + palladium, bag Gold + nickel + ruthenium, an alloy of platinum and nickel, an alloy of platinum and cobalt, an alloy of platinum and iron, and the like.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal are not included, the main component of the catalyst is preferably nickel element.

It is preferable to contain at least 1 sort (s) among nickel metal, oxide, and hydroxide.

You may add a transition metal as a 2nd component. As a 2nd component to add, it is preferable to contain at least 1 type of element among titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon.

As a preferable combination, nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, etc. are mentioned.

If necessary, an intermediate layer can be formed between the first layer 20 and the electrolytic electrode substrate 10. By providing the intermediate layer, the durability of the electrolytic electrode 100 can be improved.

As an intermediate | middle layer, what has affinity for both the 1st layer 20 and the electrode base material 10 for electrolysis is preferable. As the intermediate layer, nickel oxide, platinum group metal, platinum group metal oxide, and platinum group metal hydroxide are preferable. As an intermediate | middle layer, it can form by apply | coating and baking the solution containing the component which forms an intermediate | middle layer, and can also form a surface oxide layer by heat-processing a base material at 300-600 degreeC in air atmosphere. In addition, it can form by a well-known method, such as a thermal spraying method and an ion plating method.

(2nd floor)

As the components of the first layer 30 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals. At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included. Examples of preferred combinations of the elements included in the second layer include combinations exemplified in the first layer. The combination of a 1st layer and a 2nd layer may be a combination with the same composition, and a composition ratio differs, and the combination of a different composition may be sufficient as it.

As thickness of a catalyst layer, the sum total of the formed catalyst layer and the intermediate | middle layer has preferable 0.01 micrometer-20 micrometers. If it is 0.01 micrometer or more, it can fully function as a catalyst. If it is 20 micrometers or less, a strong catalyst layer can be formed with little fall-out from a base material. 0.05 micrometers-15 micrometers are more preferable. More preferably, they are 0.1 micrometer-10 micrometers. More preferably, they are 0.2 micrometer-8 micrometers.

As thickness of an electrode, ie, the thickness of the sum total of an electrolytic electrode base material and a catalyst layer, 315 micrometers or less are preferable, 220 micrometers or less are more preferable, 170 micrometers or less are more preferable from a viewpoint of handling property of an electrode, 150 The thickness is even more preferable, 145 µm or less is particularly preferable, 140 µm or less is still more preferable, 138 µm or less is even more preferable, and 135 µm or less is even more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, it is preferable that it is 130 micrometers or less from a viewpoint similar to the above, More preferably, it is less than 130 micrometers, More preferably, it is 115 micrometers or less, More preferably, it is 65 micrometers or less. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, the thickness of an electrode can be calculated | required by measuring with a dejimatic thickness gauge (Mitsutoyo Corporation, minimum display 0.001 mm). The thickness of the electrode base material for electrodes was measured similarly to the thickness of an electrode. The thickness of the catalyst layer can be obtained by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

(Method for producing electrode for electrolysis)

Next, one Embodiment of the manufacturing method of the electrolytic electrode 100 is described in detail. In the present embodiment, the first layer 20, preferably the second layer (on the electrode base material for electrolysis) is performed by a method such as baking (pyrolysis) of the coating film in an oxygen atmosphere or ion plating, plating, thermal spraying or the like. By forming 30), the electrode 100 for electrolysis can be manufactured. Especially, since the pyrolysis method, the plating method, and the ion plating method can form a catalyst layer, suppressing the deformation of the electrolytic electrode base material, it is preferable. If the viewpoint of productivity is further added, the plating method and the thermal decomposition method are more preferable. In this manufacturing method of the present embodiment, high productivity of the electrode 100 for electrolysis can be realized. Specifically, in the pyrolysis method, a catalyst layer is formed on an electrolytic electrode substrate by a coating step of applying a coating liquid containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing pyrolysis. Pyrolysis means here that the metal salt used as a precursor is heated and decomposed | disassembled into a metal or metal oxide and gaseous substance. Although decomposition products differ depending on the metal species used, the kind of salt, and the atmosphere in which pyrolysis is performed, most metals tend to form oxides in an oxidizing atmosphere. In the industrial production process of electrolytic electrodes, pyrolysis is usually carried out in air, and in most cases metal oxides or metal hydroxides are formed.

(Formation of the first layer of the anode)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved at least 1 sort (s) of metal salt of ruthenium, iridium, and titanium to an electrolytic electrode base material, and thermally decomposes (baking) in presence of oxygen. The content of ruthenium, iridium and titanium in the first coating liquid is approximately the same as that of the first layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may perform a baking at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. It is preferable that the pyrolysis time per one is longer, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of Second Layer of Anode)

The 2nd layer 30 is formed as needed, for example, apply | coating the solution containing a palladium compound and a platinum compound, or the solution (2nd coating liquid) containing a ruthenium compound and a titanium compound on the 1st layer 20 After that, it is obtained by pyrolysis in the presence of oxygen.

(Formation of First Layer of Cathode by Pyrolysis)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved the metal salt of various combinations to the electrode base material for electrolysis, and thermally decomposing (baking) in presence of oxygen. The content rate of the metal in a 1st coating liquid is substantially the same as the 1st layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water, ethanol, butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. It is preferable that the pyrolysis time per one is longer, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After forming the 1st layer 20, after baking for a long time as needed, if it heats for 1 to 90 minutes in the range of 350 degreeC-650 degreeC, the stability of the 1st layer 20 can be improved further. .

(Formation of intermediate layer)

An intermediate | middle layer is formed as needed, for example, is obtained by apply | coating the solution (2nd coating liquid) containing a palladium compound or a platinum compound on a base material, and then thermally decomposing in presence of oxygen. Alternatively, the nickel oxide intermediate layer may be formed on the surface of the substrate by only heating the substrate in the range of 300 ° C to 580 ° C for 1 minute to 60 minutes without applying the solution.

(Formation of First Layer of Cathode by Ion Plating)

The first layer 20 may be formed by ion plating.

As an example, the method of fixing a base material in a chamber, and irradiating an electron beam to a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and ruthenium is deposited on the substrate as ruthenium oxide.

(Formation of First Layer of Cathode by Plating)

The first layer 20 can also be formed by a plating method.

As an example, when a base material is used as a cathode and electrolytic plating is performed in the electrolyte solution containing nickel and tin, alloy plating of nickel and tin can be formed.

(Formation of First Layer of Cathode by Thermal Spray)

The first layer 20 can also be formed by thermal spraying.

As an example, by spraying nickel oxide particles on a substrate, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed.

The electrode for electrolysis of this embodiment can be used integrally with diaphragm, such as an ion exchange membrane and a microporous membrane. Therefore, it can use as a membrane integrated electrode, the work which replaces a cathode and an anode at the time of updating an electrode becomes unnecessary, and work efficiency improves significantly.

The electrode for electrolysis of this embodiment forms a membrane | film | coat and laminated body, such as an ion exchange membrane and a microporous membrane, and makes it the integral body of a membrane and an electrode, and can make electrolytic performance equivalent or improved when it is a new article. have. Although the said diaphragm will not be specifically limited if it can be set as an electrode and a laminated body, it demonstrates in detail below.

[Ion exchange membrane]

The ion exchange membrane has a membrane body containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group, and a coating layer formed on at least one side of the membrane body. In addition, the coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is 0.1 to 10 m 2 / g. The ion exchange membrane of such a structure has little influence on the electrolytic performance by the gas which generate | occur | produces during electrolysis, and can exhibit stable electrolytic performance.

The ion exchange membrane includes a sulfonic acid layer having an ion exchange group derived from a sulfo group (group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), an ion exchange group derived from a carboxyl group (group represented by -CO _2- , Hereinafter, any one of the carboxylic acid layers which have a "carboxylic acid group" is provided. In view of strength and dimensional stability, it is preferable to further have a reinforcing core material.

The inorganic particles and the binder will be described in detail in the description section of the coating layer below.

2 is a schematic cross-sectional view showing an embodiment of the ion exchange membrane. The ion exchange membrane 1 has a membrane main body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group, and coating layers 11a and 11b formed on both surfaces of the membrane main body 10.

In the ion exchange membrane 1, the membrane main body 10 includes a sulfonic acid layer 3 and a carboxylic acid layer 2, and the strength and dimensional stability are enhanced by the reinforcing core 4. Since the ion exchange membrane 1 is provided with the sulfonic acid layer 3 and the carboxylic acid layer 2, it is used suitably as an ion exchange membrane.

In addition, the ion exchange membrane may have only one of a sulfonic acid layer and a carboxylic acid layer. In addition, the ion exchange membrane does not necessarily need to be reinforced by the reinforcing core, and the arrangement state of the reinforcing core is not limited to the example of FIG. 2.

(The membrane body)

First, the membrane main body 10 constituting the ion exchange membrane 1 will be described.

The membrane main body 10 may have a function of selectively permeating cations, and may include a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group. The structure and the material thereof are not particularly limited, and a suitable one can be appropriately selected. have.

The hydrocarbon-based polymer or fluorine-containing polymer having an ion exchange group in the membrane main body 10 can be obtained from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange precursor which can be an ion-exchange group, for example, by hydrolysis or the like. Specifically, for example, the main chain is made of a fluorinated hydrocarbon, and has a group (ion exchanger precursor) which can be converted into an ion exchanger by hydrolysis or the like as a pendant side chain, and also a polymer which can be melt processed (hereinafter referred to as "fluorine-containing polymer). (a) ") to produce the precursor of the membrane main body 10, and then convert the ion exchanger precursor into the ion exchanger to obtain the membrane main body 10.

The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the third group below. have. Moreover, it can also manufacture by the homopolymerization of 1 type of monomers chosen from any of the following 1st group, the following 2nd group, and the following 3rd group.

As a monomer of a 1st group, a vinyl fluoride compound is mentioned, for example. Examples of the vinyl fluoride compound include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and the like. In particular, when the ion exchange membrane is used as the alkali electrolytic membrane, the vinyl fluoride compound is preferably a perfluoro monomer, and is perfluoro selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Monomer is preferred.

As a monomer of a 2nd group, the vinyl compound which has a functional group which can be converted into a carboxylic acid type ion exchange group (carboxylic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted to a carboxylic acid group, for example, and the like can be _{CF 2 = CF (OCF 2 CYF} ) s -O (CZF) t monomers represented by -COOR (wherein, s is 0 An integer of -2, t represents an integer of 1 to 12, Y and Z each independently represents F or CF ₃ , and R represents a lower alkyl group, for example, a lower alkyl group is an alkyl group having 1 to 3 carbon atoms. .).

Among these, CF is _{2 = CF (OCF 2 CYF)} n -O (CF 2) _m -COOR compound represented by are preferred. Here n represents an integer of 0 to 2, m represents an integer of 1 to 4, Y represents F or CF ₃ , and R represents CH ₃ , C ₂ H ₅ or C ₃ H ₇ .

When the ion exchange membrane is used as a cation exchange membrane for alkali electrolysis, it is preferable to use at least a perfluoro compound as the monomer. However, since the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis, the alkyl group ( R) may not be a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

As a monomer of a 2nd group, the monomer shown below is more preferable among the above.

CF ₂ = CFOCF ₂ -CF (CF ₃ ) OCF ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CF [OCF ₂ -CF (CF ₃ )] ₂ O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₃ COOCH ₃ .

As a monomer of a 3rd group, the vinyl compound which has a functional group which can be converted into a sulfone type ion exchange group (sulfonic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted into a sulfonic acid is, for example, CF ₂ = a monomer represented by the _{CFO-X-CF 2 -SO 2} F are preferred (wherein, X represents an alkylene group of a perfluoroalkyl.). As these specific examples, the monomer etc. which are shown below are mentioned.

CF ₂ = CFOCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CF (CF ₂ ) ₂ SO ₂ F,

CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₂ OCF ₃ ) OCF ₂ CF ₂ SO ₂ F.

Among these, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F are more preferable.

The copolymer obtained from these monomers can be manufactured by the polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, especially the general polymerization method used with respect to tetrafluoroethylene. For example, in the non-aqueous method, inert solvents such as perfluorohydrocarbon and chlorofluorocarbon are used, and in the presence of radical polymerization initiators such as perfluorocarbon peroxide and azo compound, the temperature is 0 to 200 캜 and the pressure is 0.1 to 0.1. The polymerization reaction can be carried out under the condition of 20 MPa.

In the said copolymerization, the kind and ratio of the combination of the said monomers are not specifically limited, It selects according to the kind and quantity of the functional group to provide to the fluorine-containing polymer obtained. For example, in the case of using a fluorine-containing polymer containing only a carboxylic acid group, at least one monomer may be selected and copolymerized from the first group and the second group, respectively. In the case of using a fluorine-containing polymer containing only a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group and the third group, respectively. In the case of using a fluorine-containing polymer having a carboxylic acid group and a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group, the second group, and the third group, respectively. In this case, the target fluorine-containing polymer can also be obtained by separately polymerizing the copolymer composed of the first group and the second group and the copolymer composed of the first group and the third group, and then mixing the copolymer separately. . Moreover, although the mixing ratio of each monomer is not specifically limited, When increasing the quantity of functional groups per unit polymer, what is necessary is just to increase the ratio of the monomer chosen from the said 2nd group and the 3rd group.

Although the total ion exchange capacity of a fluorine-containing copolymer is not specifically limited, It is preferable that it is 0.5-2.0 mg equivalent / g, and it is more preferable that it is 0.6-1.5 mg equivalent / g. Here, total ion exchange capacity means the equivalent of the exchanger per unit weight of dry resin, and can be measured by neutralization titration etc.

In the membrane main body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorine-containing polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorine-containing polymer having a carboxylic acid group are laminated. . By using this layer structure as the membrane main body 10, the selective permeability of cations such as sodium ions can be further improved.

In the case where the ion exchange membrane 1 is disposed in the electrolytic cell, the sulfonic acid layer 3 is usually disposed on the anode side of the electrolytic cell and the carboxylic acid layer 2 on the cathode side of the electrolytic cell.

It is preferable that the sulfonic acid layer 3 is comprised from the material with low electrical resistance, and it is preferable that a film thickness is thicker than the carboxylic acid layer 2 from a viewpoint of film strength. The film thickness of the sulfonic acid layer 3 becomes like this. Preferably it is 2-25 times of the carboxylic acid layer 2, More preferably, it is 3-15 times.

It is preferable that the carboxylic acid layer 2 has high anion exclusion property even if it is thin. Anion-exclusion here means the property which wants to interrupt the invasion and permeation | transmission of anion to the ion exchange membrane 1. In order to improve anion exclusion, disposing a carboxylic acid layer having a small ion exchange capacity with respect to the sulfonic acid layer is effective.

As the fluorine-containing polymer used for the sulfonic acid layer 3, for example, a polymer obtained by using CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F as the third group of monomers is suitable.

Carboxylic acids referred to as the fluorine-based polymer for use in sancheung (2) is, for example, as monomers of group 2 _{CF 2 = CFOCF 2 CF (CF} 2) O (CF 2) a polymer obtained by using ₂ COOCH ₃ are suitable.

(Coating layer)

The ion exchange membrane has a coating layer on at least one side of the membrane body. 2, in the ion exchange membrane 1, the coating layers 11a and 11b are formed on both surfaces of the membrane main body 10, respectively.

The coating layer includes inorganic particles and a binder.

As for the average particle diameter of an inorganic particle, it is more preferable that it is 0.90 micrometer or more. If the average particle diameter of the inorganic particles is 0.90 µm or more, the durability against impurities as well as gas adhesion is greatly improved. In other words, a particularly significant effect is obtained by increasing the average particle diameter of the inorganic particles and by satisfying the above-described specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by crushing gemstones can be used. Preferably, the inorganic particles obtained by gemstone grinding can be suitably used.

In addition, the average particle diameter of an inorganic particle can be 2 micrometers or less. If the average particle diameter of an inorganic particle is 2 micrometers or less, it can prevent that a film | membrane is damaged by an inorganic particle. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 µm.

Here, an average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation).

It is preferable that the shape of an inorganic particle is an irregular shape. Resistance to impurities is further improved. In addition, the particle size distribution of the inorganic particles is preferably wide.

It is preferable that an inorganic particle contains at least 1 sort (s) of inorganic substance chosen from the group which consists of an oxide of a group IV element of a periodic table, a nitride of a group IV element of a periodic table, and a carbide of a group IV element of a periodic table. More preferably, they are particles of zirconium oxide from the viewpoint of durability.

It is preferable that this inorganic particle is an inorganic particle manufactured by crushing the gemstone of an inorganic particle, or it is preferable to make spherical particle | grains of the uniform diameter of particle | grains into an inorganic particle by melting and refine | purifying the gemstone of an inorganic particle.

Examples of the raw material grinding method include, but are not particularly limited to, ball mills, bead mills, colloid mills, conical mills, disc mills, edge mills, milling mills, hammer mills, pellet mills, VSI mills, willy mills, roller mills, and jet mills. Etc. can be mentioned. Moreover, it is preferable to wash | clean after grinding | pulverization, and it is preferable to be acid-processed at that time. As a result, impurities such as iron adhering to the surface of the inorganic particles can be reduced.

The coating layer preferably comprises a binder. A binder is a component which keeps inorganic particle on the surface of an ion exchange membrane, and comprises a coating layer. It is preferable that a binder contains a fluorine-containing polymer from a viewpoint of resistance to electrolyte solution or the product by electrolysis.

As a binder, it is more preferable that it is a fluorine-containing polymer which has a carboxylic acid group or a sulfonic acid group from a tolerance with respect to the electrolyte solution and the product by electrolysis, and adhesiveness to the surface of an ion exchange membrane. When forming a coating layer on the layer (sulfonic acid layer) containing a fluorine-containing polymer which has a sulfonic acid group, it is more preferable to use the fluorine-containing polymer which has a sulfonic acid group as a binder of this coating layer. Moreover, when forming a coating layer on the layer (carboxylic acid layer) containing the fluorine-containing polymer which has a carboxylic acid group, it is more preferable to use the fluorine-containing polymer which has a carboxylic acid group as a binder of this coating layer.

It is preferable that it is 40-90 mass%, and, as for content of an inorganic particle in a coating layer, it is more preferable that it is 50-90 mass%. Moreover, it is preferable that it is 10-60 mass%, and, as for content of a binder, it is more preferable that it is 10-50 mass%.

The distribution density of the coating layer in the ion exchange membrane is preferably 0.05 to 2 mg per cm 2. In addition, when an ion exchange membrane has a concave-convex shape on the surface, it is preferable that the distribution density of a coating layer is 0.5-2 mg per cm <2>.

It does not specifically limit as a method of forming a coating layer, A well-known method can be used. For example, the method of apply | coating the coating liquid which disperse | distributed inorganic particle to the solution containing a binder by spray etc. is mentioned.

(Reinforced heartwood)

It is preferable that the ion exchange membrane has a reinforcing core material disposed inside the membrane body.

The reinforcing core is a member for enhancing the strength and dimensional stability of the ion exchange membrane. By arrange | positioning a reinforcing core material inside a membrane main body, especially expansion and contraction of an ion exchange membrane can be controlled to a desired range. Such an ion exchange membrane can maintain excellent dimensional stability for a long time without being stretched more than necessary in electrolysis or the like.

The configuration of the reinforcing core is not particularly limited, and may be formed by spinning a yarn called reinforcing yarn, for example. The reinforcement yarn mentioned here is a member which constitutes a reinforcing core material, which can impart desired dimensional stability and mechanical strength to the ion exchange membrane, and refers to a yarn that can stably exist in the ion exchange membrane. By using the reinforcing core material which radiated such reinforcement yarn, further excellent dimensional stability and mechanical strength can be provided to the ion exchange membrane.

The material of the reinforcing core material and the reinforcing yarn used for this is not particularly limited, but it is preferable that the material is resistant to acids, alkalis, or the like. desirable.

Examples of the fluorine-containing polymer used in the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether polymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetra Fluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, vinylidene fluoride polymer (PVDF), and the like. Among these, it is preferable to use the fiber which consists of polytetrafluoroethylene from a heat resistant and chemical resistant viewpoint especially.

The diameter of the reinforcing sand used for the reinforcing core is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The weave density (number of insertion lines per unit length) is preferably 5 to 50 lines / inch. The form of the reinforcing core is not particularly limited, and for example, a woven fabric, a nonwoven fabric, a knitted fabric, or the like is used, but it is preferably a form of a woven fabric. In addition, the thickness of the woven fabric is preferably 30 to 250 m, more preferably 30 to 150 m.

As the woven fabric or knitted fabric, monofilament, multifilament or yarns, slit yarns, and the like thereof can be used, and the weaving method can use various weaving methods such as plain weave, leno weave, knitting, cord weave, and seerker.

The weaving method and arrangement of the reinforcing core material in the membrane main body are not particularly limited and can be appropriately arranged in consideration of the size and shape of the ion exchange membrane, the desired physical properties and the use environment for the ion exchange membrane, and the like.

For example, the reinforcing core may be disposed along a predetermined direction of the membrane body, but from the viewpoint of dimensional stability, the reinforcing core is disposed along the predetermined first direction, and a second direction substantially perpendicular to the first direction is provided. Therefore, it is preferable to arrange a separate reinforcing core material. By arranging the plurality of reinforcing cores so as to run substantially straight inside the longitudinal membrane body of the membrane body, further superior dimensional stability and mechanical strength can be imparted in multiple directions. For example, an arrangement for weaving the reinforcing core material (warp) disposed along the longitudinal direction and the reinforcing core material (weft) arranged along the transverse direction on the surface of the membrane body is preferable. Lion weaved by inserting the same number of wefts into the weaving plain weave by twisting and inserting warp and weft alternately, or by weaving two warp and leno weaving by twisting two warp and two or several lines. It is more preferable to use a woven fabric (a loom) from the viewpoint of dimensional stability, mechanical strength, and ease of manufacture.

In particular, it is preferable that the reinforcing core is disposed along both directions of the MD direction (Machine Direction direction) and the TD direction (Transverse Direction direction) of the ion exchange membrane. That is, it is preferable to be woven in the MD direction and the TD direction. Here, MD direction means the direction (flow direction) in which a membrane main body and various core materials (for example, a reinforced core material, a reinforcement yarn, a sacrificial yarn etc. mentioned later) are conveyed in the manufacturing process of the ion exchange membrane mentioned later, and a TD direction is It refers to a direction approximately perpendicular to the MD direction. The yarn woven along the MD direction is called MD yarn, and the yarn woven along the TD direction is called TD yarn. Usually, the ion exchange membrane used for electrolysis is rectangular, and a longitudinal direction becomes MD direction, and the width direction becomes a TD direction in many cases. By weaving the reinforced MD core material and the reinforced TD core material, it is possible to give even more excellent dimensional stability and mechanical strength in multiple directions.

The spacing of the reinforcing cores is not particularly limited, and may be appropriately arranged in consideration of desired physical properties, use environment, and the like for the ion exchange membrane.

The opening ratio of the reinforcing core material is not particularly limited, and is preferably 30% or more, more preferably 50% or more and 90% or less. The opening ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane.

The opening ratio of the reinforcing core is the total area (B) of the surface through which substances such as ions (electrolyte and cation (for example, sodium ions) contained) in the area (A) of either surface of the membrane body can pass. The ratio of (B / A). The total area (B) of the surface through which substances such as ions can pass can be referred to as the total area of the region where cations, electrolytes, and the like are not blocked by the reinforcing core included in the ion exchange membrane.

3 is a schematic view for explaining the opening ratio of the reinforcing core material constituting the ion exchange membrane. FIG. 3 enlarges a part of the ion exchange membrane and shows only the arrangement of the reinforcing cores 21 and 22 in the region, and the illustration of the other members is omitted.

The total area C of the reinforcement core from the area A of the region including the area of the reinforcement core, which is also surrounded by the reinforcement core 21 arranged in the longitudinal direction and the reinforcement core 22 arranged in the horizontal direction. By subtracting, the total area B of the area through which substances such as ions in the area A of the area can pass can be obtained. That is, an opening ratio can be calculated | required by following formula (I).

Aperture ratio = (B) / (A) = ((A)-(C)) / (A). (I)

Among the reinforcing cores, a particularly preferable form is a tape yarn or a highly oriented monofilament containing PTFE in view of chemical resistance and heat resistance. Specifically, a high-strength porous sheet made of PTFE is a tape yarn slitted in tape form, or a 50 to 300 denier of a highly oriented monofilament made of PTFE, and a woven density of 10 to 50 lines / inch. It is more preferable that it is a reinforcement core material whose thickness is the range of 50-100 micrometers. It is more preferable that the opening ratio of the ion exchange membrane including such a reinforcing core material is 60% or more.

Examples of the shape of the reinforcing yarn include round yarns and tape-like yarns.

(Communication hole)

It is preferable that the ion exchange membrane has a communication hole inside the membrane main body.

The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, a communication hole is a tubular hole formed in the inside of a membrane main body, and is formed by eluting the sacrificial core material (or sacrificial thread) mentioned later. The shape and diameter of the communication hole can be controlled by selecting the shape and diameter of the sacrificial core material (sacrificial yarn).

By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured at the time of electrolysis. Although the shape of a communication hole is not specifically limited, According to the manufacturing method mentioned later, it can be set as the shape of the sacrificial core material used for formation of a communication hole.

The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With such a structure, in the part where the communication hole is formed in the cathode side of the reinforcing core material, ions (for example, sodium ions) transported through the electrolyte solution filled in the communication hole can also flow to the cathode side of the reinforcing core material. As a result, since the flow of cation is not blocked, the electrical resistance of the ion exchange membrane can be made lower.

The communication hole may be formed along only one predetermined direction of the membrane main body constituting the ion exchange membrane, but is formed in both the longitudinal direction and the transverse direction of the membrane main body in view of exhibiting more stable electrolytic performance. desirable.

[Production method]

As a suitable manufacturing method of an ion exchange membrane, the method of having the following (1) process-(6) process is mentioned.

(1) Process: The process of manufacturing the fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(2) Process: If necessary, a sacrificial yarn is disposed between adjacent reinforcing cores by at least weaving a plurality of reinforcing cores and a property of dissolving in an acid or alkali and forming at least a communication hole. To obtain the finished reinforcement.

(3) Process: The process of film-forming the said fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(4) Step: The step of embedding the reinforcing material in the film as necessary to obtain a membrane body having the reinforcing material disposed therein.

(5) Process: The process (hydrolysis process) of hydrolyzing the membrane main body obtained at process (4). (6) Process: The process (coating process) of forming a coating layer in the film main body obtained at the process (5).

Hereinafter, each process is explained in full detail.

(1) Process: process for producing fluorine-containing polymer

In the step (1), the fluorine-containing polymer is produced by using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of a fluorine-containing polymer, in the manufacture of the fluorine-containing polymer which forms each layer, the mixing ratio of the monomer of a raw material may be adjusted.

(2) Process: manufacturing process of reinforcement

A reinforcing material is a woven fabric etc. which woven the reinforcement yarn. The reinforcing material is embedded in the film to form the reinforcing core material. When using an ion exchange membrane having communication holes, the sacrificial yarn is also woven into the reinforcing material. In this case, the blending amount of the sacrificial material is preferably 10 to 80 mass%, more preferably 30 to 70 mass% of the entire reinforcing material. By weaving a sacrificial thread, the mesh shift | offset of a reinforcement core material can also be prevented.

The sacrificial material has solubility in a film production process or an electrolytic environment, and rayon, polyethylene terephthalate (PET), cellulose, polyamide, and the like are used. Moreover, polyvinyl alcohol etc. which have a thickness of 20-50 denier and consist of monofilament or multifilament are also preferable.

In the step (2), by adjusting the arrangement of the reinforcing core material or the sacrificial material, the opening ratio, the arrangement of the communication holes, and the like can be controlled.

(3) process: filming process

In the step (3), the fluorine-containing polymer obtained in the step (1) is filmed using an extruder. A single layer structure may be sufficient as a film, and as above-mentioned, the two-layered structure of a sulfonic acid layer and a carboxylic acid layer may be sufficient, and the multilayered structure of three or more layers may be sufficient as it.

As a method of film-forming, the following are mentioned, for example.

A method of filming each of the fluorine-containing polymer having a carboxylic acid group and the fluorine-containing polymer having a sulfonic acid group separately.

A method in which a fluorine-containing polymer having a carboxylic acid group and a fluorine-containing polymer having a sulfonic acid group are co-extruded into a composite film.

In addition, a plurality of films may be sufficient respectively. Moreover, coextrusion of different kinds of films is preferable because it contributes to raising the adhesive strength of an interface.

(4) step: the step of obtaining the membrane body

In the step (4), the film body in which the reinforcing material is embedded is obtained by embedding the reinforcing material obtained in the step (2) inside the film obtained in the step (3).

As a preferable formation method of a film main body, (i) the fluorine-containing polymer which has a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) located in the cathode side (henceforth, the layer which consists of this is called a 1st layer), And forming a fluorine-containing polymer having a sulfonic acid group precursor (e.g., a sulfonylfluoride functional group) (hereinafter, referred to as a second layer) by a coextrusion method, and heating and vacuum source as necessary. Is laminated on a flat plate or drum having a large number of pores on the surface of the reinforcing material and the second layer / first layer composite film in the order of a reinforcing material and a heat-resistant release paper having air permeability. Integrating while removing air between each layer by decompression under temperature; (ii) Apart from the second layer / first layer composite film, the fluorine-containing polymer (third layer) having a sulfonic acid group precursor is previously filmed alone, and the surface is heated and heated using a vacuum source if necessary. The laminated film was laminated in the order of a composite film consisting of a third layer film, a reinforcing core material, and a second layer / first layer via a heat-resistant release paper having air permeability on a flat plate or a drum having a large number of pores thereon. The method of integrating, removing the air between each layer by pressure reduction under the temperature which melt | dissolves is mentioned.

Here, coextrusion of a 1st layer and a 2nd layer contributes to raising the adhesive strength of an interface.

Moreover, the method of integrating under reduced pressure has the feature that the thickness of the 3rd layer on a reinforcement material becomes large compared with the pressure press method. In addition, since the reinforcing material is fixed to the inner surface of the membrane main body, it has the performance of sufficiently maintaining the mechanical strength of the ion exchange membrane.

In addition, the variation of lamination described here is an example, and considering the desired layer structure, physical properties, etc. of a film body, a suitable lamination pattern (for example, the combination of each layer, etc.) can be selected, and then co-extruded.

Further, in order to further improve the electrical performance of the ion exchange membrane, a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is further interposed between the first layer and the second layer. It is also possible to use a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor instead of the layer.

The method for forming the fourth layer may be a method of separately preparing a fluorine-containing polymer having a carboxylic acid group precursor and a fluorine-containing polymer having a sulfonic acid group precursor, and then mixing the monomers with the carboxylic acid group precursor and the sulfonic acid group precursor. The method of copolymerizing the monomer which has the thing may be used.

In the case where the fourth layer is configured as an ion exchange membrane, the coextruded film of the first layer and the fourth layer is molded, and the third layer and the second layer are filmed independently of this, by the method described above. You may laminate | stack and three layers of a 1st layer / 4th layer / 2nd layer may be film-formed by coextrusion at once.

In this case, the direction in which the extruded film flows is the MD direction. In this way, a membrane body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material.

In addition, the ion exchange membrane preferably has a protruding portion, that is, a convex portion, made of a fluorine-containing polymer having a sulfonic acid group, on the surface side of the sulfonic acid layer. It does not specifically limit as a method of forming such a convex part, The well-known method of forming a convex part in the resin surface can be employ | adopted. Specifically, the method of embossing on the surface of a film main body is mentioned, for example. For example, when the said composite film, reinforcing material, etc. are integrated, the said convex part can be formed by using the release paper previously embossed. When forming a convex part by embossing, control of the height and placement density of a convex part can be performed by controlling the emboss shape (shape of a release paper) to be transferred.

(5) hydrolysis process

In the step (5), the membrane body obtained in the step (4) is hydrolyzed to convert the ion exchanger precursor into the ion exchanger (hydrolysis step).

In the step (5), the elution hole can be formed in the membrane main body by dissolving and removing the sacrificial yarn contained in the membrane main body with an acid or an alkali. In addition, the sacrificial yarn may remain in the communication hole without being completely dissolved and removed. In addition, the sacrificial yarn remaining in the communication hole may be dissolved and removed by the electrolytic solution when the ion exchange membrane is provided for electrolysis.

The sacrificial yarn is soluble in acid or alkali in the ion exchange membrane production process or in an electrolytic environment, and communication holes are formed in the site by dissolving the sacrificial material.

The step (5) can be performed by immersing the membrane body obtained in the step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (dimethyl sulfoxide) can be used.

It is preferable that this mixed solution contains 2.5-4.0 N of KOH, and contains 25-35 mass% of DMSO.

As temperature of hydrolysis, it is preferable that it is 70-100 degreeC. The higher the temperature, the thicker the apparent thickness. More preferably, it is 75-100 degreeC.

It is preferable that it is 10 to 120 minutes as time of hydrolysis. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes.

Here, the process of forming a communication hole by eluting a sacrificial yarn is demonstrated in detail. 4 (a) and 4 (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane.

In FIGS. 4A and 4B, only the communication holes 504 formed by the reinforcement yarns 52, the sacrificial yarns 504a, and the sacrificial yarns 504a are shown. The illustration is omitted.

First, the reinforcement yarn 52 which comprises a reinforcing core material in an ion exchange membrane, and the sacrificial yarn 504a for forming the communication hole 504 in an ion exchange membrane are used as a knitted reinforcement material. And the communication hole 504 is formed by eluting the sacrificial yarn 504a in the process (5).

According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a may be adjusted in accordance with the arrangement of the reinforcing core and the communication hole in the membrane main body of the ion exchange membrane.

In FIG. 4A, although the reinforcement of the plain weave which woven the reinforcement yarn 52 and the sacrificial yarn 504a in both the longitudinal direction and the transverse direction in the ground is illustrated, the reinforcement yarn in the reinforcement material as needed. The arrangement of the 52 and the victim 504a can be changed.

(6) coating process

In the step (6), the coating layer can be formed by preparing a coating liquid containing the inorganic particles obtained by gemstone grinding or melting of the gemstone and a binder, and applying and drying the coating liquid on the surface of the ion exchange membrane obtained in the step (5). .

As a binder, after hydrolyzing the fluorine-containing polymer having an ion exchange group precursor with an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH), it is immersed in hydrochloric acid to replace the counter ion of the ion exchange group with H ⁺ . One binder (eg, a fluorine-containing polymer having a carboxyl or sulfo group) is preferred. Since it becomes easy to melt | dissolve in water and ethanol mentioned later by this, it is preferable.

This binder is dissolved in a solution in which water and ethanol are mixed. Moreover, the preferable volume ratio of water and ethanol is 10: 1-1:10, More preferably, it is 5: 1-1: 5, More preferably, it is 2: 1-1: 2. In the solution thus obtained, the inorganic particles are dispersed by a ball mill to obtain a coating solution. At this time, the average particle diameter of a particle | grains, etc. can also be adjusted by adjusting the time and the rotation speed at the time of dispersion. In addition, the preferable compounding quantity of an inorganic particle and a binder is as above-mentioned.

The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, but is preferably a light coating liquid. Thereby, it becomes possible to apply | coat uniformly to the surface of an ion exchange membrane.

In addition, when dispersing the inorganic particles, a surfactant may be added to the dispersion. As surfactant, a nonionic surfactant is preferable, For example, HS-210, NS-210, P-210, E-212 by Nichi-yu Corporation, etc. are mentioned.

An ion exchange membrane is obtained by apply | coating the obtained coating liquid to the surface of an ion exchange membrane by spray coating or roll coating.

[Microporous membrane]

As described above, the microporous membrane of the present embodiment is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various microporous membranes can be applied.

Although the porosity of the microporous membrane of this embodiment is not specifically limited, For example, it can be 20-90, Preferably it is 30-85. The porosity can be calculated by the following formula, for example.

Porosity = (1- (Dry Film Weight in Dry State) / (Volume calculated from the thickness, width and length of the film and weight calculated from the density of the film material)) × 100

Although the average pore diameter of the microporous membrane of this embodiment is not specifically limited, For example, it can be 0.01 micrometer-10 micrometers, Preferably it is 0.05 micrometer-5 micrometers. The average pore diameter is, for example, the film is vertically cut in the thickness direction, and the cut surface is observed by FE-SEM. It can obtain | require by measuring and averaging about 100 points of the diameter of the hole observed.

Although the thickness of the microporous film of this embodiment is not specifically limited, For example, it can be 10 micrometers-1000 micrometers, Preferably it is 50 micrometers-600 micrometers. The said thickness can be measured using a micrometer (made by Mitsutoyo Corporation) etc., for example.

Specific examples of the microporous membranes described above include Agir's Zirfon Perl UTP 500 (also referred to as Zirfon membrane in this embodiment), International Publication No. 2013-183584, International Publication No. 2016-203701, etc. The things described are mentioned.

[Laminated body]

The laminated body of this embodiment is equipped with the electrode for electrolysis of this embodiment, and the diaphragm or feeder which contact | connects the said electrode for electrolysis. Since it is comprised in this way, the laminated body of this embodiment can improve the work efficiency at the time of electrode update in an electrolytic cell, and can express the outstanding electrolytic performance after an update.

That is, when the electrode is updated by the laminate of the present embodiment, the electrode can be updated by the same simple operation as the update of the diaphragm without involving complicated work such as peeling off the electrode fixed to the electrolytic cell. Work efficiency is greatly improved.

Moreover, according to the laminated body of this invention, the performance at the time of a new article of electrolytic performance can be maintained or improved. In addition, even when only a feeder is provided in a new electrolytic cell (that is, when an electrode without a catalyst layer is provided), the electrolytic electrode of the present embodiment can act as an electrode only by sticking to the feeder. As a result, it is possible to significantly reduce or zero the catalyst coating.

The laminated body of this embodiment can be stored, transported to a customer, etc. in the state wound (for example, roll shape) wound on the pipe made from vinyl chloride etc., and handling becomes easy easily.

In addition, as the electric power feeder in this embodiment, various base materials mentioned later, such as a deteriorated electrode (namely, an existing electrode) and an electrode without a catalyst coating, can be applied.

In the laminate of the present embodiment, the force applied per unit mass and unit area of the electrolytic electrode to the diaphragm or feeder is preferably 0.08 N / (mg · cm 2) or more, more preferably 0.1 N / (mg · cm 2) or more, more preferably 0.14 N / (mg · cm 2) or more, and even more preferably, handling in a large size (for example, size 1.5 m × 2.5 m) becomes easier. Is 0.2 N / (mg · cm 2) or more. Although an upper limit is not specifically limited, It is preferable that it is 1.6 N / (mg * cm <2>) or less, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred.

[Winding body]

The wound body of this embodiment includes the electrode for electrolysis of this embodiment, or the laminated body of this embodiment. That is, the wound body of this embodiment is formed by winding the electrode for electrolysis of this embodiment, or the laminated body of this embodiment. Like the winding body of this embodiment, handling property can be improved more by winding up and size-down the electrode for electrolysis of this embodiment, or the laminated body of this embodiment.

[Electrolysis tank]

The electrolytic cell of this embodiment contains the electrode for electrolysis of this embodiment. EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of an electrolytic cell is explained in full detail, for example, when salt electrolysis is performed using an ion exchange membrane as a diaphragm.

[Electrolysis cell]

5 is a cross-sectional view of the electrolytic cell 1.

The electrolytic cell 1 includes the anode chamber 10, the cathode chamber 20, the partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, and the anode provided in the anode chamber 10. 11 and a cathode 21 provided in the cathode chamber 20. If necessary, the base 18a and the reverse current absorbing layer 18b formed on the base 18a may be provided, and the reverse current absorber 18 provided in the cathode chamber may be provided. The positive electrode 11 and the negative electrode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 has the following cathode structure. The negative electrode structure 40 includes a negative electrode chamber 20, a negative electrode 21 provided in the negative electrode chamber 20, and a reverse current absorber 18 provided in the negative electrode chamber 20, and the reverse current absorber 18. 9 has a base 18a and a reverse current absorbing layer 18b formed on the base 18a, and the cathode 21 and the reverse current absorbing layer 18b are electrically connected to each other. The negative electrode chamber 20 further includes a current collector 23, a support 24 supporting the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the electrical power collector 23 and the negative electrode 21. The support body 24 is provided between the collector 23 and the partition 30. The current collector 23 is electrically connected to the negative electrode 21 via the metal elastic body 22. The partition 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition 30, the support body 24, the collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected to each other. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be connected indirectly via a current collector, a support, a metal elastic body, a partition, or the like. It is preferable that the whole surface of the cathode 21 is covered with a catalyst layer for the reduction reaction. In addition, in the form of electrical connection, the partition 30 and the support body 24, the support body 24 and the collector 23, the collector 23 and the metal elastic body 22 are respectively directly attached, and the metal elastic body 22 ) May be laminated on the cathode 21. Welding etc. are mentioned as a method of attaching these structural members directly to each other. In addition, the reverse current absorber 18, the negative electrode 21, and the current collector 23 may be collectively referred to as the negative electrode structure 40.

6 is a cross-sectional view of two electrolytic cells 1 adjacent in the electrolytic cell 4. 7 shows the electrolytic cell 4. 8 shows a step of assembling the electrolytic cell 4. As shown in FIG. 6, the electrolytic cells 1, the cation exchange membrane 2, and the electrolytic cells 1 are arranged in series in this order. The ion exchange membrane 2 is arrange | positioned between the anode chamber of one electrolytic cell 1 and the cathode chamber of the other electrolytic cell 1 among two electrolytic cells which adjoin in an electrolytic cell. In other words, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are spaced apart by the cation exchange membrane 2. As shown in FIG. 7, the electrolytic cell 4 is composed of a plurality of electrolytic cells 1 connected in series via an ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 8, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series via an ion exchange membrane 2 and being connected by a press 5.

The electrolytic cell 4 has the positive terminal 7 and the negative terminal 6 connected to a power supply. The positive electrode 11 of the electrolytic cell 1 positioned at the shortest of the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4 is electrically connected to the positive electrode terminal 7. Among the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4, the negative electrode 21 of the electrolytic cell located at the end opposite to the positive electrode terminal 7 is electrically connected to the negative electrode terminal 6. The electric current at the time of electrolysis flows toward the negative electrode terminal 6 from the positive terminal 7 side via the positive electrode and the negative electrode of each electrolytic cell 1. Moreover, you may arrange | position the electrolytic cell (anode terminal cell) which has only an anode chamber, and the electrolytic cell (cathode terminal cell) which has only a cathode chamber in the both ends of the electrolytic cell 1 which connected. In this case, the positive terminal 7 is connected to the positive terminal cell disposed at one end thereof, and the negative terminal 6 is connected to the negative terminal cell arranged at the other end thereof.

In the case of electrolysis of brine, brine is supplied to each anode chamber 10, and pure or low concentration aqueous sodium hydroxide solution is supplied to the cathode chamber 20. Each liquid is supplied to each electrolytic cell 1 from electrolyte supply pipe (not shown) via electrolyte supply hose (not shown). In addition, electrolyte solution and the product by electrolysis are collect | recovered from an electrolyte collection pipe (not shown). In electrolysis, sodium ions in brine move from the anode chamber 10 of one electrolytic cell 1 through the ion exchange membrane 2 to the cathode chamber 20 of the neighboring electrolytic cell 1. Therefore, the current during electrolysis flows along the direction in which the electrolytic cells 1 are connected in series. That is, the current flows from the anode chamber 10 toward the cathode chamber 20 via the cation exchange membrane 2. By electrolysis of the brine, chlorine gas is produced on the anode 11 side, and sodium hydroxide (solute) and hydrogen gas are produced on the cathode 21 side.

(Positive room)

The anode chamber 10 includes a cathode 11 or an anode feeder 11. When the electrode for electrolysis of this embodiment is inserted in the anode side, 11 functions as a positive electrode feeder. When the electrode for electrolysis of this embodiment is not inserted in the anode side, 11 functions as an anode. In addition, the anode chamber 10 is disposed on an anode side electrolyte supply portion for supplying an electrolyte solution to the anode chamber 10 and an anode side electrolyte supply portion, and a baffle plate disposed to be substantially parallel or oblique with the partition wall 30. And it is preferable to have an anode side gas-liquid separation part arrange | positioned above the baffle plate and isolate | separates a gas from the electrolyte solution which gas mixed.

(anode)

When the electrode for electrolysis of this embodiment is not inserted in the anode side, the anode 11 is provided in the frame of the anode chamber 10. As the anode 11, a metal electrode such as so-called DSA (registered trademark) can be used. DSA is a titanium-based electrode whose surface was covered with an oxide containing ruthenium, iridium and titanium.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Positive electrode feeder)

When the electrode for electrolysis of this embodiment is inserted in the anode side, the positive electrode feeder 11 is provided in the frame of the anode chamber 10. As the positive electrode feeder 11, a metal electrode such as DSA (registered trademark) or the like may be used, or titanium without a catalyst coating may be used. It is also possible to use DSA with a thinner catalyst coating thickness. Moreover, the used anode can also be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Anode-side electrolyte supply unit)

The anode-side electrolyte supply unit supplies the electrolyte solution to the anode chamber 10 and is connected to the electrolyte solution supply pipe. It is preferable that an anode side electrolyte supply part is arrange | positioned under the anode chamber 10. As an anode side electrolyte supply part, the pipe (dispersion pipe) etc. which have an opening part formed in the surface can be used, for example. It is more preferable that such a pipe is arrange | positioned in parallel with the bottom part 19 of an electrolysis cell along the surface of the anode 11. This pipe is connected to the electrolyte supply pipe (liquid supply nozzle) which supplies electrolyte solution in the electrolysis cell 1. The electrolyte solution supplied from the liquid supply nozzle is conveyed to the electrolysis cell 1 by the pipe, and is supplied to the inside of the anode chamber 10 from the opening provided in the surface of the pipe. By arranging the pipes parallel to the bottom portion 19 of the electrolytic cell along the surface of the anode 11, the electrolyte can be uniformly supplied into the anode chamber 10, which is preferable.

(Positive side gas-liquid separator)

It is preferable that the anode-side gas-liquid separator is disposed above the baffle plate. During electrolysis, the anode-side gas-liquid separator has a function of separating the generated gas such as chlorine gas and the electrolyte. In addition, unless otherwise indicated, an upper side means the upward direction in the electrolysis cell 1 of FIG. 5, and a lower side means the downward direction in the electrolysis cell 1 of FIG.

At the time of electrolysis, when the generated gas and electrolyte generated in the electrolytic cell 1 become mixed phase (gas-liquid mixed phase) and discharged out of the system, vibration occurs due to pressure fluctuation inside the electrolytic cell 1, and physical damage of the ion exchange membrane is prevented. I may cause it. In order to suppress this, it is preferable that the positive electrode side gas-liquid separation part for separating a gas and a liquid is provided in the electrolysis cell 1 of this embodiment. It is preferable that a defoaming plate for removing bubbles is provided in the anode-side gas-liquid separator. When a gas-liquid mixture flows through a vesicle plate, a bubble bursts and can be isolate | separated into electrolyte solution and gas. As a result, vibration during electrolysis can be prevented.

(Baffle version)

It is preferable that the baffle plate is disposed above the anode-side electrolyte supply portion, and is disposed substantially parallel to or inclined with the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. By providing the baffle plate, the electrolyte solution (salt water, etc.) can be circulated internally in the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged to be spaced apart from the space near the anode 11 and the space near the partition wall 30. From this viewpoint, the baffle plate is preferably provided so as to face each surface of the anode 11 and the partition wall 30. In the space near the anode partitioned by the baffle plate, electrolytic solution concentration (saline concentration) decreases as electrolysis proceeds, and product gas such as chlorine gas is generated. Thereby, the specific gravity difference of gas-liquid arises in the space near the anode 11 divided by the baffle plate, and the space near the partition 30. As shown in FIG. By using this, the internal circulation of the electrolyte solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolyte solution in the anode chamber 10 can be made more uniform.

Although not shown in FIG. 5, a current collector may be separately provided inside the anode chamber 10. As such an electrical power collector, it can also be set as the material and structure similar to the electrical power collector of the negative electrode chamber mentioned later. In the anode chamber 10, the anode 11 itself can also function as a current collector.

(septum)

The partition 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition 30 may be called a separator and divides the anode chamber 10 and the cathode chamber 20. As the partition 30, a well-known thing can be used as a separator for electrolysis, For example, the partition which welded the plate which consists of nickel to the cathode side, and titanium to the anode side, etc. are mentioned.

(Cathode room)

The negative electrode chamber 20 functions as a negative electrode feeder when the electrolytic electrode of the present embodiment is inserted into the negative electrode side, and 21 when the electrolytic electrode of the present embodiment is not inserted into the negative electrode side. Functions as a cathode. When the reverse current absorber is provided, the negative electrode or the negative electrode feeder 21 and the reverse current absorber are electrically connected to each other. In addition, it is preferable that the cathode chamber 20 also has a cathode side electrolyte solution supply section and a cathode side gas-liquid separation section similarly to the anode chamber 10. In addition, description is abbreviate | omitted about the same thing as each part which comprises the anode chamber 10 among each site | part which comprises the cathode chamber 20. As shown in FIG.

(cathode)

When the electrode for electrolysis of this embodiment is not inserted in the cathode side, the cathode 21 is provided in the frame of the cathode chamber 20. It is preferable that the negative electrode 21 has a catalyst layer which covers a nickel substrate and a nickel substrate. As a component of the catalyst layer on the nickel substrate, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd , Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho And metals such as Er, Tm, Yb and Lu, and oxides or hydroxides of the metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may give reduction process to the negative electrode 21 as needed. As the base material of the negative electrode 21, one in which nickel, nickel alloy, iron, or stainless steel is plated with nickel may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Cathode feeder)

When the electrode for electrolysis of this embodiment is inserted in the cathode side, the cathode feeder 21 is provided in the frame of the cathode chamber 20. The catalyst component may be coated on the negative electrode feeder 21. The catalyst component may be originally used as a negative electrode and remain. As components of the catalyst layer, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Metals, such as Tm, Yb, Lu, and the oxide or hydroxide of this metal are mentioned. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. As the base material of the negative electrode feeder 21, a plated nickel on nickel, a nickel alloy, iron or stainless may be used.

In the feeder 21, a nickel-plated nickel, nickel alloy, iron, or stainless steel may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

Reverse Current Absorption Layer

A material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected as the material of the reverse current absorbing layer. For example, nickel, iron, etc. are mentioned.

(Current collector)

The negative electrode chamber 20 preferably includes a current collector 23. This increases the current collecting effect. In the present embodiment, the current collector 23 is a porous plate, and is preferably disposed substantially parallel to the surface of the negative electrode 21.

The current collector 23 is preferably made of an electrically conductive metal such as nickel, iron, copper, silver, titanium, or the like. The current collector 23 may be a mixture of these metals, an alloy or a composite oxide. In addition, as long as it is a shape which functions as an electrical power collector, the shape of the electrical power collector 23 may be any shape, and plate-shaped or network-shaped may be sufficient as it.

(Metal elastomer)

By providing the metal elastic body 22 between the collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, The distance between each anode 11 and each cathode 21 can be shortened, and the voltage applied to the entire plurality of electrolytic cells 1 connected in series can be lowered. By lowering the voltage, the total consumption can be reduced. Moreover, when the metal elastic body 22 is provided and the laminated body containing the electrolytic electrode which concerns on this invention is installed in an electrolytic cell, the said electrode for electrolysis is pressed by the pressure which the metal elastic body 22 presses. It can be kept in place stably.

As the metallic elastic body 22, a spring member, such as a spiral spring and a coil, a cushion mat, etc. can be used. As the metal elastic body 22, a suitable one can be appropriately adopted in consideration of a stress or the like which presses the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the collector 23 on the cathode chamber 20 side, or may be provided on the surface of the partition wall on the anode chamber 10 side. Usually, since both chambers are partitioned so that the cathode chamber 20 becomes smaller than the anode chamber 10, from the viewpoint of the strength of the frame or the like, the metal elastic body 22 is used for the current collector 23 of the cathode chamber 20. It is preferable to provide between and the cathode 21. Moreover, it is preferable that the metal elastic body 22 consists of metal which has electrical conductivity, such as nickel, iron, copper, silver, titanium.

(Support)

The negative electrode chamber 20 preferably includes a support 24 for electrically connecting the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently.

The support 24 is preferably made of a metal having electrical conductivity such as nickel, iron, copper, silver, titanium, or the like. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod, plate, or network. The support body 24 is plate-shaped, for example. The plurality of supports 24 are disposed between the partition wall 30 and the current collector 23. The plurality of supports 24 are arranged such that their respective surfaces are parallel to each other. The support body 24 is disposed substantially perpendicular to the partition wall 30 and the current collector 23.

(Anode side gasket, cathode side gasket)

It is preferable that the anode side gasket is arranged on the surface of the frame body constituting the anode chamber 10. It is preferable that the cathode side gasket is arrange | positioned at the surface of the frame body which comprises the cathode chamber 20. As shown in FIG. The electrolytic cells are connected so that the anode side gasket which one electrolytic cell is equipped, and the cathode side gasket of the electrolysis cell adjacent to this pinch | interpose the ion exchange membrane 2 (refer FIG. 5, 6). By these gaskets, when connecting a plurality of electrolytic cells 1 in series via the ion exchange membrane 2, airtightness can be provided to a connection location.

A gasket seals between an ion exchange membrane and an electrolysis cell. As a specific example of a gasket, a frame-shaped rubber sheet etc. in which the opening part was formed in the center are mentioned. The gasket is required to be resistant to corrosive electrolytes, generated gases and the like and to be used for a long time. Therefore, from the viewpoint of chemical resistance and hardness, vulcanized products, peroxide crosslinked products and the like of ethylene propylene diene rubber (EPDM rubber) and ethylene propylene rubber (EPM rubber) are usually used as the gasket. Moreover, the gasket which coat | covered the area | region (contact part) which contact | connects a liquid as needed with fluororesin, such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether polymer (PFA), can also be used. These gaskets should just have opening parts, respectively, so that the flow of electrolyte solution may not be disturbed, The shape is not specifically limited. For example, a frame-shaped gasket is bonded with an adhesive or the like along the circumferential edge of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20. For example, when connecting two electrolytic cells 1 via the ion exchange membrane 2 (refer FIG. 6), when each electrolytic cell 1 which bonded the gasket through the ion exchange membrane 2 is fastened, do. Thereby, it can suppress that an electrolyte solution, the alkali metal hydroxide produced by electrolysis, chlorine gas, hydrogen gas, etc. leak to the exterior of the electrolysis cell 1.

(Ion exchange membrane (2))

As the ion exchange membrane 2, it is as described in the term of the said ion exchange membrane.

(Hydraulic)

In the electrolytic cell of this embodiment, the electrolytic cell in the case of performing electrolytic electrolysis has the structure which changed the ion exchange membrane in the electrolytic cell in the case of performing the above-mentioned salt electrolysis to a microporous membrane. In addition, since the raw material to be supplied is water, it differs from the electrolytic cell in the case of performing the above-mentioned salt electrolysis. As for other configurations, the same configuration as the electrolytic cell in the case of performing salt electrolysis can also be adopted. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. However, in the case of hydrolysis, since oxygen gas is only generated in the anode chamber, the same material as the cathode chamber is used. Can be used. For example, nickel etc. can be mentioned. In addition, the anode coating is suitably a catalyst coating for oxygen generation. Examples of catalyst coatings include metals, oxides, hydroxides, and the like of platinum group metals and transition metals. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used.

Second Embodiment

Here, the 2nd Embodiment of this invention is described in detail, referring FIGS. 22-42.

[Laminated body]

The laminate of the second embodiment (hereinafter, simply referred to as "the present embodiment" in the term of <second embodiment>) includes an electrode for electrolysis, a diaphragm or a feeder in contact with the electrode for electrolysis, and The force applied per unit mass and unit area of the electrolytic electrode to the membrane or feeder is less than 1.5 N / mg · cm 2. Since it is comprised in this way, the laminated body of this embodiment can improve the work efficiency at the time of electrode update in an electrolytic cell, and can express the outstanding electrolytic performance after an update.

That is, with the laminated body of this embodiment, when updating an electrode, an electrode can be updated by the simple operation similar to the update of a diaphragm, without involving complicated operations, such as peeling the existing electrode fixed to the electrolysis cell. Therefore, the work efficiency is greatly improved.

Moreover, according to the laminated body of this invention, the performance at the time of a new article of electrolytic performance can be maintained or improved. Therefore, the electrode fixed to the conventional new electrolytic cell and functioning as a positive electrode and a negative electrode only needs to function as a feeder, and the catalyst coating can be greatly reduced or zero.

The laminated body of this embodiment can be stored, transported to a customer, etc. in the state wound (for example, roll shape) wound on the pipe made from vinyl chloride etc., and handling becomes easy easily.

In addition, as the electric power feeder in this embodiment, various base materials mentioned later, such as a deteriorated electrode (that is, an existing electrode) and an electrode without a catalyst coating, can be applied.

In addition, the laminated body of this embodiment may have a fixed part in a part as long as it has the said structure. That is, when the laminated body of this embodiment has a fixed part, if the part which does not have the said fixed is used for a measurement, and the force applied per unit mass and unit area of the electrolytic electrode obtained is less than 1.5 N / mg * cm <2>, do.

[Electrode Electrode]

The electrode for electrolysis of this embodiment can obtain favorable handling property, and has a unit mass from a viewpoint of having favorable adhesive force with a diaphragm, such as an ion exchange membrane and a microporous membrane, a feeder (a deteriorated electrode and a catalyst uncoated electrode), etc. The force applied per unit area is less than 1.5 N / mg · cm 2, preferably 1.2 N / mg · cm 2 or less, and more preferably 1.20 N / mg · cm 2 or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, More preferably, it is 1.0 N / mg * cm <2> or less, More preferably, it is 1.00 N / mg * cm <2>. It is as follows.

From the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and even more preferably 0.1 N / mg · cm 2 or more. More preferably, it is 0.14 N / (mg * cm <2>) or more. 0.2 N / (mg * cm <2>) or more is more preferable from a viewpoint of the ease of handling in a large size (e.g., size 1.5 m x 2.5 m).

The said applied force can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, arithmetic mean surface roughness, etc., for example. More specifically, for example, when the porosity is increased, the applied force tends to be small, and when the porosity is decreased, the applied force tends to be large.

In addition, good handling properties can be obtained, good adhesion to diaphragms such as ion exchange membranes and microporous membranes, deteriorated electrodes, catalyst uncoated feeders and the like, and from the viewpoint of economy, the mass per unit area is 48 mg / cm 2 or less. It is preferable, More preferably, it is 30 mg / cm <2> or less, More preferably, it is 20 mg / cm <2> or less, It is preferable that it is 15 mg / cm <2> or less from a comprehensive viewpoint which combined handling property, adhesiveness, and economics. Although a lower limit is not specifically limited, For example, it is about 1 mg / cm <2>.

The said mass per unit area can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, etc., for example. More specifically, for example, if the thickness is the same, the mass per unit area tends to be smaller when the porosity is increased, and the mass per unit area tends to be larger when the porosity is reduced.

The force applied can be measured by the following method (i) or (ii) and is as having described in the Example in detail. The force applied is the value obtained by the measurement of the method (i) (also called "the applied force 1") and the value obtained by the measurement of the method (ii) (also called the "the applied force 2"). Although this may be same or different, any value becomes less than 1.5 N / mg * cm <2>.

[Method (i)]

Nickel plate obtained by blasting with alumina of particle number 320 (thickness 1.2 mm, width 200 mm) and an ion exchange membrane coated with inorganic particles and a binder on both sides of a membrane of a perfluorocarbon polymer into which an ion exchanger was introduced (horizontal 170 mm in length and the details of the ion-exchange membrane here, as described in the Example) and an electrode sample (130 mm in length) were laminated in this order, and this laminated body was fully immersed in pure water, and then laminated body. A sample for measurement is obtained by removing excess moisture adhering to the surface. In addition, the arithmetic mean surface roughness Ra of the nickel plate after a blasting process is 0.5-0.8 micrometer. The specific calculation method of arithmetic mean surface roughness Ra is as having described in the Example.

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were raised in 10 mm in the vertical direction. Measure the weight when This measurement is performed three times to calculate an average value.

The average value is divided by the area of the overlapped portion of the electrode sample and the ion exchange membrane and the mass of the electrode sample of the overlapped portion with the ion exchange membrane, and the force applied per unit mass and unit area (1) (N / mg · cm 2) To calculate.

The force (1) applied per unit mass and unit area obtained by the method (i) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. From the viewpoint of having a ratio of less than 1.5 N / mg · cm 2, it is preferably 1.2 N / mg · cm 2 or less, more preferably 1.20 N / mg · cm 2 or less, still more preferably 1.1 N / mg · cm 2 or less. More preferably, it is 1.10 N / mg * cm <2> or less, More preferably, it is 1.0 N / mg * cm <2> or less, More preferably, it is 1.00 N / mg * cm <2> or less. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more and more preferably 0.14 N / (mg · cm 2) and 0.2 N / (mg · cm 2) from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m). ) Is more preferable.

When the electrode 1 for electrolysis of the present embodiment is satisfied, it can be used integrally with a diaphragm such as an ion exchange membrane or a microporous membrane or a feeder (that is, as a laminate). The work of replacing the negative electrode and the positive electrode fixed to the electrolytic cell by, for example, welding is unnecessary, and the work efficiency is greatly improved. In addition, by using the electrode for electrolysis of this embodiment as a laminated body integrated with an ion exchange membrane, a microporous membrane, or a power feeder, electrolytic performance can be made equivalent to or improved in the case of a new article.

When shipping a new electrolytic cell, the catalyst coating was conventionally coated on the electrode fixed to the electrolytic cell, but since it can be used as an electrode only by combining the electrolytic electrode of this embodiment with the electrode which does not have a catalyst coating, catalyst coating It is possible to greatly reduce or zero the amount of the production process and the catalyst to achieve this. The conventional electrode, in which the catalyst coating is significantly reduced or zero, can be electrically connected to the electrode for electrolysis of the present embodiment and function as a feeder for flowing a current.

[Method (ii)]

The nickel plate (thickness 1.2 mm, width 200 mm, the same nickel plate as the method (i)) and the electrode sample (length 130 mm) obtained by blasting with alumina of particle number 320 were laminated in this order. After fully immersing the laminate with pure water, a sample for measurement is obtained by removing excess moisture adhering to the laminate surface. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were 10 mm in the vertical direction. The weight at the time of rise is measured. This measurement is performed three times to calculate an average value.

This average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate, and the mass of the electrode sample in the overlapped portion of the nickel plate, and the adhesive force 2 per unit mass and unit area (N / mg · cm 2) is obtained. Calculate.

The force (2) applied per unit mass and unit area obtained by the method (ii) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. From the viewpoint of having a ratio of less than 1.5 N / mg · cm 2, it is preferably 1.2 N / mg · cm 2 or less, more preferably 1.20 N / mg · cm 2 or less, still more preferably 1.1 N / mg · cm 2 or less. More preferably, it is 1.10 N / mg * cm <2> or less, More preferably, it is 1.0 N / mg * cm <2> or less, More preferably, it is 1.00 N / mg * cm <2> or less. From the viewpoint of further improving the electrolytic performance, it is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, still more preferably 0.1 N / (mg · cm 2) As mentioned above, More preferably, it is more preferably 0.14 N / (mg * cm <2>) or more from a viewpoint that handling by a large size (for example, size 1.5m * 2.5m) becomes easy.

When the force 2 applied by the electrode for electrolysis of this embodiment is satisfied, it can be stored, transported to a customer, etc. in the state wound (for example, roll type) wound on the pipe made from vinyl chloride, etc., and handling becomes large. It becomes easy. In addition, by adhering the electrode for electrolysis of this embodiment to a laminated body by deteriorating the existing electrode, electrolytic performance can be made equivalent to or improved in the case of a new article.

If the electrode for electrolysis of this embodiment is an electrode with a large elastic deformation area, better handling property can be obtained, and it will provide better adhesive force, such as a diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode, an uncoated feeder, etc. From the viewpoint of having, the thickness of the electrolytic electrode is preferably 315 µm or less, more preferably 220 µm or less, still more preferably 170 µm or less, even more preferably 150 µm or less, and particularly preferably 145 µm or less. 140 micrometers or less are more preferable, 138 micrometers or less are further more preferable, and 135 micrometers or less are further more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, from a viewpoint similar to the above, 130 micrometers or less are preferable, less than 130 micrometers are more preferable, 115 micrometers or less are more preferable, and 65 micrometers or less are still more preferable. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, in this embodiment, a "elastic deformation area | region is wide" means that it is difficult to produce the curvature resulting from winding after winding an electrode for electrolysis to make a winding body, and canceling a wound state. In addition, the thickness of an electrode for electrolysis means the thickness which combined the electrode base material for electrolysis and a catalyst layer, when including the catalyst layer mentioned later.

It is preferable that the electrolytic electrode of this embodiment contains an electrolytic electrode base material and a catalyst layer. Although the thickness (gauge thickness) of the said electrolytic electrode base material is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feedstock), and an electrode without a catalyst coating (grade 300 micrometers or less are preferable from a viewpoint of having a good adhesive force with the whole), and being rolled suitably, being able to bend it favorably, and facilitating handling in a large size (e.g., size 1.5 m x 2.5 m). 205 micrometers or less are more preferable, 155 micrometers or less are more preferable, 135 micrometers or less are still more preferable, 125 micrometers or less are still more preferable, 120 micrometers or less are still more preferable, 100 micrometers or less are further more preferable In addition, from a viewpoint of handling property and economical efficiency, 50 micrometers or less are further more preferable. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In this embodiment, a liquid is interposed between a diaphragm, such as an ion exchange membrane and a microporous membrane, and a metal porous plate or metal plate (that is, a feeder), such as an electrode or a deteriorated existing electrode or an uncoated catalyst electrode, and an electrolytic electrode. It is desirable to be. Any liquid may be used as long as the liquid generates surface tension such as water and an organic solvent. The greater the surface tension of the liquid, the greater the force exerted between the diaphragm and the electrode for electrolysis or between the metal porous plate or the metal plate and the electrode for electrolysis. Therefore, a liquid having a high surface tension is preferable. Examples of the liquid include the following (the numerical values in parentheses indicate the surface tension of the liquid at 20 ° C).

Hexane (20.44 mN / m), Acetone (23.30 mN / m), Methanol (24.00 mN / m), Ethanol (24.05 mN / m), Ethylene glycol (50.21 mN / m), Water (72.76 mN / m)

If the liquid has a large surface tension, the diaphragm and the electrode for electrolysis, or the metal porous plate or the metal plate (feeder), and the electrode for electrolysis are integrated (to be laminated) to facilitate electrode update. The liquid between the diaphragm and the electrode for electrolysis, or the metal porous plate or the metal plate (feeder), and the electrode for electrolysis should be such that the amount of adhesion between the electrodes depends on the surface tension, and as a result, the amount of liquid is small. Even if it is mixed with the electrolyte after installation in the cell, it does not affect the electrolysis itself.

From a practical point of view, it is preferable to use the liquid whose surface tension is 24 mN / m-80 mN / m, such as ethanol, ethylene glycol, water, as a liquid. In particular, an aqueous solution obtained by dissolving caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like in water or alkali is preferable. Moreover, surface tension can also be adjusted by including surfactant in these liquids. By including surfactant, the adhesiveness of a diaphragm and an electrode for electrolysis, or a metal porous plate or a metal plate (feeder), and an electrode for electrolysis changes, and handling property can be adjusted. There is no restriction | limiting in particular as surfactant, Both an ionic surfactant and a nonionic surfactant can be used.

Although the electrode for electrolysis of this embodiment is not specifically limited, favorable handling property can be obtained, and it is favorable with the diaphragm, such as an ion exchange membrane and a microporous membrane, deteriorated electrode (feeder), and an uncoated catalyst (feeder). It is preferable that the ratio measured by the following method (2) is 90% or more from a viewpoint of adhesive force, It is more preferable that it is 92% or more, and also in a large size (for example, size 1.5 m x 2.5 m) It is more preferable that it is 95% or more from a viewpoint that handling becomes easy. The upper limit is 100%.

[Method (2)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the condition of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 280 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis of this embodiment is not specifically limited, favorable handling property can be obtained, and it is favorable with the diaphragm, such as an ion exchange membrane and a microporous membrane, deteriorated electrode (feeder), and an uncoated catalyst (feeder). It is preferable that the ratio measured by the following method (3) is 75% or more, It is more preferable that it is 80% or more from a viewpoint that it has adhesive force, can be rolled suitably, and can be bent favorably, and also large size It is more preferable that it is 90% or more from a viewpoint that handling in (for example, size 1.5 m x 2.5 m) becomes easy. The upper limit is 100%.

[Method (3)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 145 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis of this embodiment is not specifically limited, favorable handling property can be obtained, and it is favorable with a diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an uncoated catalyst (feeder). It is preferable that it has an adhesive force and is a porous structure from a viewpoint of the prevention of the residence of the gas which arises during electrolysis, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80% or less, still more preferably 20 to 75%.

In addition, an opening ratio is a ratio of an opening part per unit volume. The calculation method varies depending on whether the opening is also considered to submicron order or only the visible opening. In this embodiment, the volume V was calculated from the values of the gauge thickness, the width, and the length of the electrode, and the weight W was measured, and the porosity A was calculated by the following formula.

A = (1- (W / (V × ρ)) × 100

ρ is the density (g / cm 3) of the material of the electrode. For example, nickel is 8.908 g / cm 3 and titanium is 4.506 g / cm 3. The adjustment of the porosity is to change the area punching the metal per unit area if the punching metal, change the SW (short diameter), LW (long diameter), the feeding value if the expanded metal, the mesh diameter of the metal fiber, By changing the number of meshes, changing the pattern of the photoresist to be used for electroforming, changing the metal fiber diameter and fiber density for nonwoven fabrics, and changing the mold for forming the voids for the foamed metal, etc. Adjust

As for the electrode for electrolysis in this embodiment, it is preferable that the value measured by the following method (A) is 40 mm or less from a viewpoint of handling property, More preferably, it is 29 mm or less, More preferably, it is 10 mm It is below, More preferably, it is 6.5 mm or less. In addition, the specific measuring method is as having described in the Example.

[Method (A)]

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, a sample obtained by laminating an ion exchange membrane and the electrolytic electrode was wound and fixed on a curved surface of a vinyl chloride core material having an outer diameter of φ 32 mm, and left standing for 6 hours. Later, when the electrolytic electrode was separated and placed on a horizontal plate, the heights L ₁ and L ₂ in the vertical direction at both ends of the electrolytic electrode were measured, and these average values were measured.

The electrolytic electrode in this embodiment makes the electrolytic electrode 50 mm x 50 mm in size, and has a temperature of 24 degreeC, a relative humidity of 32%, a piston speed of 0.2 cm / s, and an airflow of 0.4 cc / cm <2> / s. In one case (hereinafter, also referred to as "measurement condition 1"), the ventilation resistance (hereinafter also referred to as "airflow resistance 1") is preferably 24 kPa · s / m or less. High ventilation resistance means that air is difficult to flow, and indicates a high density. In this state, since the product by electrolysis stays in the electrode and the reaction substrate becomes difficult to diffuse into the electrode, the electrolytic performance (voltage, etc.) tends to be deteriorated. In addition, the concentration of the film surface tends to increase. Specifically, the caustic concentration tends to increase on the cathode side, and the supplyability of brine tends to decrease on the anode side. As a result, the product remains at a high concentration at the interface where the membrane and the electrode contact, leading to damage of the membrane, leading to voltage rise and film damage on the cathode surface and film damage on the anode surface. In this embodiment, in order to prevent such a problem, it is preferable to make a ventilation resistance 24 kPa * s / m or less. It is more preferable that it is less than 0.19 kPa * s / m from a viewpoint similar to the above, It is still more preferable that it is 0.15 kPa * s / m or less, It is still more preferable that it is 0.07 kPa * s / m or less.

In addition, in this embodiment, when the ventilation resistance is greater than or equal to a certain level, in the case of the negative electrode, NaOH generated at the electrode tends to remain at the interface between the electrode and the diaphragm, resulting in a high concentration. In order to prevent the damage to the diaphragm which may occur due to such retention, it is preferably less than 0.19 kPa · s / m, more preferably 0.15 kPa · s / m or less. And it is more preferable that it is 0.07 kPa * s / m or less.

On the other hand, when the airflow resistance is low, the area of the electrode is small, so that the electrolytic area is small and the electrolytic performance (voltage, etc.) tends to be deteriorated. When the ventilation resistance is zero, since the electrode for electrolysis is not provided, a power supply functions as an electrode and there exists a tendency for electrolytic performance (voltage etc.) to deteriorate remarkably. In this regard, the lower limit specified as the ventilation resistance 1 is not particularly limited, but is preferably more than 0 kPa · s / m, more preferably 0.0001 kPa · s / m or more, still more preferably 0.001 kPa S / m or more.

In addition, the ventilation resistance 1 may not be able to obtain sufficient measurement accuracy in 0.07 kPa * s / m or less on the measuring method. In view of this, for the electrode for electrolysis having a ventilation resistance 1 of 0.07 kPa · s / m or less, the ventilation resistance according to the following measuring method (hereinafter also referred to as “measurement condition 2”) (hereinafter also referred to as “airflow resistance 2”) Evaluation by is also possible. That is, the ventilation resistance 2 sets the electrode for electrolysis to the size of 50 mm x 50 mm, and it is the ventilation | emission when the temperature is 24 degreeC, the relative humidity 32%, the piston speed 2 cm / s, and the ventilation amount 4 cc / cm <2> / s. Resistance.

The measuring method of specific ventilation resistance 1 and 2 is as having described in the Example.

The ventilation resistances 1 and 2 can be in the above ranges by appropriately adjusting the porosity, electrode thickness, and the like described later, for example. More specifically, for example, when the pore rate is increased, the airflow resistances 1 and 2 tend to be small, and when the porosity is small, the airflow resistances 1 and 2 tend to be large.

In the electrolytic electrode of the present embodiment, as described above, the force applied per unit mass and unit area of the electrolytic electrode to the diaphragm or feeder is less than 1.5 N / mg · cm 2. Thus, the electrode for electrolysis of this embodiment can comprise a laminated body with a diaphragm or a feeder by contacting a diaphragm or a feeder (for example, the existing anode or cathode in an electrolytic cell, etc.) with moderate adhesive force. . In other words, it is not necessary to firmly bond the diaphragm or the feeder and the electrode for electrolysis by a complicated method such as thermocompression bonding, and the surface tension derived from moisture, which may be included in the diaphragm such as an ion exchange membrane or a microporous membrane, for example. Since it adheres only by weak force, and becomes a laminated body, a laminated body can be comprised easily in any scale. Moreover, since such a laminated body expresses excellent electrolytic performance, the laminated body of this embodiment is suitable for electrolytic use, For example, it can use especially preferably for the use of the member of an electrolytic cell, or the update of the said member.

EMBODIMENT OF THE INVENTION Hereinafter, one form of the electrode for electrolysis of this embodiment is demonstrated.

It is preferable that the electrolytic electrode which concerns on this embodiment contains an electrolytic electrode base material and a catalyst layer. The catalyst layer may be composed of a plurality of layers as described below or may have a single layer structure.

As shown in FIG. 22, the electrolytic electrode 100 according to the present embodiment includes a pair of first layers 20 covering both surfaces of the electrolytic electrode substrate 10 and the electrolytic electrode substrate 10. It is provided. It is preferable that the 1st layer 20 coat | covers the electrolytic electrode base material 10 whole. As a result, the catalytic activity and durability of the electrode for electrolysis tends to be improved. In addition, the first layer 20 may be laminated only on one surface of the electrode base 10 for electrolysis.

In addition, as shown in FIG. 22, the surface of the first layer 20 may be covered with the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, only one surface of the first layer 20 may be laminated on the second layer 30.

(Electrode base for electrolysis)

The electrolytic electrode substrate 10 is not particularly limited, but a valve metal such as nickel, nickel alloy, stainless steel or titanium may be used, and at least one selected from nickel (Ni) and titanium (Ti) may be used. It is preferable to include the element of a species.

When stainless steel is used in a high concentration aqueous alkali solution, considering that iron and chromium are eluted, and that the electrical conductivity of stainless steel is about 1/10 of nickel, the electrolytic electrode substrate includes nickel (Ni). The substrate is preferred.

In addition, when the electrolytic electrode base material 10 is used in the chlorine gas generation | occurence atmosphere in the high concentration saline solution near saturation, it is preferable that a material is titanium with high corrosion resistance.

There is no restriction | limiting in particular in the shape of the electrode base material 10 for electrolysis, An appropriate shape can be selected according to the objective. As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used. Especially, a punching metal or an expanded metal is preferable. In addition, electroforming is a technique which manufactures a metal thin film of a precise pattern by combining photolithography and an electroplating method. It is a method of pattern-forming with a photoresist on a board | substrate, electroplating to the part which is not protected by a resist, and obtaining metal foil.

The shape of the electrode base material for electrolysis has suitable specifications depending on the distance between the anode and the cathode in the electrolytic cell. Although not particularly limited, in the case where the anode and the cathode have a finite distance, an expanded metal or a punched metal shape can be used, and in the case of a so-called zero gap electrolytic cell in which the ion exchange membrane and the electrode are in contact, a woven mesh woven with fine lines , Wire mesh, foamed metal, metal nonwoven fabric, expanded metal, punched metal, metal porous foil and the like can be used.

Examples of the electrode base 10 for electrolysis include a metal porous foil, a wire mesh, a metal nonwoven fabric, a punching metal, an expanded metal or a foamed metal.

As a board | plate material before processing with a punching metal and an expanded metal, the board | plate material roll-molded, electrolytic foil, etc. are preferable. It is preferable that the electrolytic foil is further plated with the same element as the base material as post-treatment to form irregularities on one or both surfaces.

In addition, it is preferable that the thickness of the electrolytic electrode base material 10 is 300 micrometers or less as mentioned above, It is more preferable that it is 205 micrometers or less, It is more preferable that it is 155 micrometers or less, It is further more preferable that it is 135 micrometers or less, 125 It is still more preferable that it is micrometer or less, It is still more preferable that it is 120 micrometers or less, It is still more preferable that it is 100 micrometers or less, It is further more preferable that it is 50 micrometers or less from a viewpoint of handling property and economy. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In the electrode base for electrolysis, it is preferable to relieve the residual stress at the time of processing by annealing the electrode base for electrolysis in an oxidizing atmosphere. Moreover, in order to improve the adhesiveness with the catalyst layer coat | covered with the said surface, the surface of an electrolytic electrode base material uses unevenness | corrugation using a steel grid, alumina powder, etc., and it is preferable to increase a surface area by acid treatment after that. Do. Or it is preferable to plating by the same element as a base material, and to increase a surface area.

In order to make the surface of the 1st layer 20 and the electrode base material 10 for electrolysis adhere to the electrode base material 10 for electrolysis, it is preferable to perform the process which increases a surface area. Examples of the treatment for increasing the surface area include a blast treatment using a cut wire, a steel grid, an alumina grid, and the like, an acid treatment using sulfuric acid or hydrochloric acid, a plating treatment using the same element as the substrate, and the like. Although arithmetic mean surface roughness Ra of the surface of a base material is not specifically limited, 0.05 micrometer-50 micrometers are preferable, 0.1-10 micrometers is more preferable, 0.1-8 micrometers is still more preferable.

Next, the case where the electrode for electrolysis of this embodiment is used as a salt electrolytic anode is demonstrated.

(1st floor)

In FIG. 22, the 1st layer 20 which is a catalyst layer contains at least 1 sort (s) of oxide of ruthenium oxide, iridium oxide, and titanium oxide. Of ruthenium oxide RuO _2, etc., it may be mentioned. IrO ₂ etc. are mentioned as an iridium oxide. Examples of titanium oxides include TiO ₂ . The first layer 20 preferably contains two kinds of oxides of ruthenium oxide and titanium oxide, or three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide. Thereby, the 1st layer 20 becomes a more stable layer, and also adhesiveness with the 2nd layer 30 improves more.

In the case where the first layer 20 includes two kinds of oxides of ruthenium oxide and titanium oxide, titanium contained in the first layer 20 with respect to one mole of ruthenium oxide included in the first layer 20. It is preferable that it is 1-9 mol, and, as for an oxide, it is more preferable that it is 1-4 mol. By setting the composition ratio of the two kinds of oxides in this range, the electrolytic electrode 100 exhibits excellent durability.

When the first layer 20 includes three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide, the first layer 20 is included in the first layer 20 with respect to one mole of ruthenium oxide contained in the first layer 20. It is preferable that it is 0.2-3 mol, and, as for the iridium oxide used, it is more preferable that it is 0.3-2.5 mol. Moreover, it is preferable that it is 0.3-8 mol, and, as for 1 mol of titanium oxide contained in the 1st layer 20 with respect to 1 mol of ruthenium oxide contained in the 1st layer 20, it is more preferable. By making the composition ratio of three types of oxides into this range, the electrode 100 for electrolysis shows the outstanding durability.

When the 1st layer 20 contains at least 2 types of oxide chosen from a ruthenium oxide, an iridium oxide, and a titanium oxide, it is preferable that these oxides form a solid solution. By forming the oxide solid solution, the electrolytic electrode 100 exhibits excellent durability.

In addition to the above composition, as long as it contains at least one oxide of ruthenium oxide, iridium oxide and titanium oxide, those having various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like, referred to as DSA (registered trademark), may be used as the first layer 20.

The first layer 20 does not need to be a single layer, but may include a plurality of layers. For example, the first layer 20 may include a layer containing three kinds of oxides and a layer containing two kinds of oxides. 0.05-10 micrometers is preferable and, as for the thickness of the 1st layer 20, 0.1-8 micrometers is more preferable.

(2nd floor)

It is preferable that the 2nd layer 30 contains ruthenium and titanium. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

It is preferable that the 2nd layer 30 contains palladium oxide, the solid solution of palladium oxide, and platinum, or the alloy of palladium and platinum. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

The longer the longer the thickness of the second layer 30 can maintain the electrolytic performance, the thickness of the second layer 30 is preferably 0.05 to 3 m.

Next, the case where the electrode for electrolysis of this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

As a component of the first layer 20 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal include at least one kind, the alloy containing the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide and the platinum group metal is platinum, palladium, rhodium, It is preferable to contain at least 1 type of platinum group metal among ruthenium and iridium.

As a platinum group metal, it is preferable to contain platinum.

It is preferable that a platinum group metal oxide contains ruthenium oxide.

It is preferable that a platinum group metal hydroxide contains a ruthenium hydroxide.

As a platinum group metal alloy, it is preferable to include the alloy of platinum, nickel, iron, and cobalt.

Moreover, it is preferable to contain the oxide or hydroxide of a lanthanoid element as a 2nd component as needed. As a result, the electrolytic electrode 100 exhibits excellent durability.

The oxide or hydroxide of the lanthanoid-based element preferably contains at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium.

Moreover, it is preferable to contain the oxide or hydroxide of a transition metal as a 3rd component as needed.

By adding the third component, the electrolytic electrode 100 exhibits more excellent durability and can reduce the electrolytic voltage.

Examples of preferred combinations include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + platinum + palladium Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium + Sulfur, Ruthenium + Lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + samarium + cobalt, ruthenium + samarium + gallium, ruthenium + samarium + gallium, ruthenium + Samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + Nickel + palladium, bag Gold + nickel + ruthenium, an alloy of platinum and nickel, an alloy of platinum and cobalt, an alloy of platinum and iron, and the like.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal are not included, the main component of the catalyst is preferably nickel element.

It is preferable to contain at least 1 sort (s) among nickel metal, oxide, and hydroxide.

You may add a transition metal as a 2nd component. As a 2nd component to add, it is preferable to contain at least 1 type of element among titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon.

As a preferable combination, nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, etc. are mentioned.

If necessary, an intermediate layer can be formed between the first layer 20 and the electrolytic electrode substrate 10. By providing the intermediate layer, the durability of the electrolytic electrode 100 can be improved.

As an intermediate | middle layer, what has affinity for both the 1st layer 20 and the electrode base material 10 for electrolysis is preferable. As the intermediate layer, nickel oxide, platinum group metal, platinum group metal oxide, and platinum group metal hydroxide are preferable. As an intermediate | middle layer, it can form by apply | coating and baking the solution containing the component which forms an intermediate | middle layer, and can also form a surface oxide layer by heat-processing a base material at 300-600 degreeC in air atmosphere. In addition, it can form by a well-known method, such as a thermal spraying method and an ion plating method.

(2nd floor)

As the components of the first layer 30 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included. Examples of preferred combinations of the elements included in the second layer include combinations exemplified in the first layer. The combination of a 1st layer and a 2nd layer may be a combination with the same composition, and a composition ratio differs, and the combination of a different composition may be sufficient as it.

As thickness of a catalyst layer, the sum total of the formed catalyst layer and the intermediate | middle layer has preferable 0.01 micrometer-20 micrometers. If it is 0.01 micrometer or more, it can fully function as a catalyst. If it is 20 micrometers or less, a strong catalyst layer can be formed with little fall-out from a base material. 0.05 micrometers-15 micrometers are more preferable. More preferably, they are 0.1 micrometer-10 micrometers. More preferably, they are 0.2 micrometer-8 micrometers.

As thickness of the electrode for electrodes, ie, the thickness of the sum total of an electrolytic electrode base material and a catalyst layer, 315 micrometers or less are preferable from a viewpoint of the handling property of an electrolytic electrode, 220 micrometers or less are more preferable, and 170 micrometers or less are further It is preferable, 150 micrometers or less are still more preferable, 145 micrometers or less are especially preferable, 140 micrometers or less are still more preferable, 138 micrometers or less are still more preferable, 135 micrometers or less are further more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, it is preferable that it is 130 micrometers or less from a viewpoint similar to the above, More preferably, it is less than 130 micrometers, More preferably, it is 115 micrometers or less, More preferably, it is 65 micrometers or less. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, the thickness of an electrode can be calculated | required by measuring with a dejimatic thickness gauge (Mitsutoyo Corporation, minimum display 0.001 mm). The thickness of the electrode base material for electrodes can be measured similarly to the thickness of the electrode for electrodes. The thickness of the catalyst layer can be obtained by subtracting the thickness of the electrode base for electrolysis from the thickness of the electrode for electrodes.

(Method for producing electrode for electrolysis)

Next, one Embodiment of the manufacturing method of the electrolytic electrode 100 is described in detail.

In the present embodiment, the first layer 20, preferably the second layer (on the electrode base material for electrolysis) is performed by a method such as baking (pyrolysis) of the coating film in an oxygen atmosphere or ion plating, plating, thermal spraying or the like. By forming 30), the electrode 100 for electrolysis can be manufactured. In this manufacturing method of the present embodiment, high productivity of the electrode 100 for electrolysis can be realized. Specifically, a catalyst layer is formed on the electrode base material for electrolysis by a coating step of applying a coating liquid containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing pyrolysis. Pyrolysis means here that the metal salt used as a precursor is heated and decomposed | disassembled into a metal or metal oxide and gaseous substance. Although decomposition products differ depending on the metal species used, the kind of salt, and the atmosphere in which pyrolysis is performed, most metals tend to form oxides in an oxidizing atmosphere. In the industrial production process of electrodes, pyrolysis is usually carried out in air, and in most cases metal oxides or metal hydroxides are formed.

(Formation of the first layer of the anode)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved at least 1 sort (s) of metal salt of ruthenium, iridium, and titanium to an electrolytic electrode base material, and thermally decomposes (baking) in presence of oxygen. The content of ruthenium, iridium and titanium in the first coating liquid is approximately the same as that of the first layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of the second layer)

The 2nd layer 30 is formed as needed, for example, apply | coating the solution containing a palladium compound and a platinum compound, or the solution (2nd coating liquid) containing a ruthenium compound and a titanium compound on the 1st layer 20 After that, it is obtained by pyrolysis in the presence of oxygen.

(Formation of First Layer of Cathode by Pyrolysis)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved the metal salt of various combinations to the electrode base material for electrolysis, and thermally decomposing (baking) in presence of oxygen. The content rate of the metal in a 1st coating liquid is substantially the same as the 1st layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of intermediate layer)

An intermediate | middle layer is formed as needed, for example, is obtained by apply | coating the solution (2nd coating liquid) containing a palladium compound or a platinum compound on a base material, and then thermally decomposing in presence of oxygen. Alternatively, the nickel oxide intermediate layer may be formed on the surface of the substrate only by heating the substrate without applying the solution.

(Formation of First Layer of Cathode by Ion Plating)

The first layer 20 may be formed by ion plating.

As an example, the method of fixing a base material in a chamber, and irradiating an electron beam to a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and ruthenium is deposited on the substrate as ruthenium oxide.

(Formation of First Layer of Cathode by Plating)

The first layer 20 can also be formed by a plating method.

As an example, when a base material is used as a cathode and electrolytic plating is performed in the electrolyte solution containing nickel and tin, alloy plating of nickel and tin can be formed.

(Formation of First Layer of Cathode by Thermal Spray)

The first layer 20 can also be formed by thermal spraying.

As an example, by spraying nickel oxide particles on a substrate, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed.

The electrode for electrolysis of this embodiment can be used integrally with diaphragm, such as an ion exchange membrane and a microporous membrane. Therefore, it can use as a membrane integrated electrode, the work which replaces a cathode and an anode at the time of updating an electrode becomes unnecessary, and work efficiency improves significantly.

Moreover, according to the integral electrode with the diaphragm, such as an ion exchange membrane and a microporous membrane, electrolytic performance can be made to be equivalent to the performance at the time of new, or it can improve.

Hereinafter, the ion exchange membrane will be described in detail.

[Ion exchange membrane]

The ion exchange membrane has a membrane body containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group, and a coating layer formed on at least one side of the membrane body. In addition, the coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is 0.1 to 10 m 2 / g. The ion exchange membrane of such a structure has little influence on the electrolytic performance by the gas which generate | occur | produces during electrolysis, and can exhibit stable electrolytic performance.

The membrane of the perfluorocarbon polymer into which the ion exchange group is introduced is a sulfonic acid layer having an ion exchange group derived from a sulfo group (group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and an ion exchange group derived from a carboxyl group. It is provided with either a carboxylic sancheung having a - (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). In view of strength and dimensional stability, it is preferable to further have a reinforcing core material.

The inorganic particles and the binder will be described in detail in the description section of the coating layer below.

It is a cross-sectional schematic diagram which shows one Embodiment of an ion exchange membrane. The ion exchange membrane 1 has a membrane main body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group, and coating layers 11a and 11b formed on both surfaces of the membrane main body 10.

In the ion exchange membrane 1, the membrane main body 10 is a sulfonic acid layer 3 having an ion exchange group derived from a sulfo group (a group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and ions derived from a carboxyl group. exchanger has a strength and dimensional stability are enhanced by the carboxylic sancheung 2 provided, and the reinforcement core (4) having a (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). Since the ion exchange membrane 1 is provided with the sulfonic acid layer 3 and the carboxylic acid layer 2, it is suitably used as a cation exchange membrane.

In addition, the ion exchange membrane may have only one of a sulfonic acid layer and a carboxylic acid layer. In addition, the ion exchange membrane does not necessarily need to be reinforced by the reinforcing core, and the arrangement state of the reinforcing core is not limited to the example of FIG. 23.

(The membrane body)

First, the membrane main body 10 constituting the ion exchange membrane 1 will be described.

The membrane main body 10 may have a function of selectively permeating cations, and may include a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group. The structure and the material thereof are not particularly limited, and a suitable one can be appropriately selected. have.

The hydrocarbon-based polymer or fluorine-containing polymer having an ion exchange group in the membrane main body 10 can be obtained from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange precursor which can be an ion-exchange group, for example, by hydrolysis or the like. Specifically, for example, the main chain is made of a fluorinated hydrocarbon, and has a group (ion exchanger precursor) which can be converted into an ion exchanger by hydrolysis or the like as a pendant side chain, and also a polymer which can be melt processed (hereinafter referred to as "fluorine-containing polymer). (a) ") to produce the precursor of the membrane main body 10, and then convert the ion exchanger precursor into the ion exchanger to obtain the membrane main body 10.

The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the third group below. have. Moreover, it can also manufacture by the homopolymerization of 1 type of monomers chosen from any of the following 1st group, the following 2nd group, and the following 3rd group.

As a monomer of a 1st group, a vinyl fluoride compound is mentioned, for example. Examples of the vinyl fluoride compound include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and the like. In particular, when the ion exchange membrane is used as the alkali electrolytic membrane, the vinyl fluoride compound is preferably a perfluoro monomer, and is perfluoro selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Monomer is preferred.

As a monomer of a 2nd group, the vinyl compound which has a functional group which can be converted into a carboxylic acid type ion exchange group (carboxylic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted to a carboxylic acid group, for example, and the like can be _{CF 2 = CF (OCF 2 CYF} ) s -O (CZF) t monomers represented by -COOR (wherein, s is 0 An integer of -2, t represents an integer of 1 to 12, Y and Z each independently represents F or CF ₃ , and R represents a lower alkyl group, for example, a lower alkyl group is an alkyl group having 1 to 3 carbon atoms. .).

Among these, CF is _{2 = CF (OCF 2 CYF)} n -O (CF 2) _m -COOR compound represented by are preferred. Here n represents an integer of 0 to 2, m represents an integer of 1 to 4, Y represents F or CF ₃ , and R represents CH ₃ , C ₂ H ₅ or C ₃ H ₇ .

When the ion exchange membrane is used as a cation exchange membrane for alkali electrolysis, it is preferable to use at least a perfluoro compound as the monomer. However, since the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis, the alkyl group ( R) may not be a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

As a monomer of a 2nd group, the monomer shown below is more preferable among the above.

CF ₂ = CFOCF ₂ -CF (CF ₃ ) OCF ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CF [OCF ₂ -CF (CF ₃ )] ₂ O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₃ COOCH ₃ .

As a monomer of a 3rd group, the vinyl compound which has a functional group which can be converted into a sulfone type ion exchange group (sulfonic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted into a sulfonic acid is, for example, CF ₂ = a monomer represented by the _{CFO-X-CF 2 -SO 2} F are preferred (wherein, X represents an alkylene group of a perfluoroalkyl.). As these specific examples, the monomer etc. which are shown below are mentioned.

CF ₂ = CFOCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CF (CF ₂ ) ₂ SO ₂ F,

CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₂ OCF ₃ ) OCF ₂ CF ₂ SO ₂ F.

Among these, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F are more preferable.

The copolymer obtained from these monomers can be manufactured by the polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, especially the general polymerization method used with respect to tetrafluoroethylene. For example, in the non-aqueous method, inert solvents such as perfluorohydrocarbon and chlorofluorocarbon are used, and in the presence of radical polymerization initiators such as perfluorocarbon peroxide and azo compound, the temperature is 0 to 200 캜 and the pressure is 0.1 to 0.1. The polymerization reaction can be carried out under the condition of 20 MPa.

In the said copolymerization, the kind and ratio of the combination of the said monomers are not specifically limited, It selects according to the kind and quantity of the functional group to provide to the fluorine-containing polymer obtained. For example, in the case of using a fluorine-containing polymer containing only a carboxylic acid group, at least one monomer may be selected and copolymerized from the first group and the second group, respectively. In the case of using a fluorine-containing polymer containing only a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group and the third group, respectively. In the case of using a fluorine-containing polymer having a carboxylic acid group and a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group, the second group, and the third group, respectively. In this case, the target fluorine-containing polymer can also be obtained by separately polymerizing the copolymer composed of the first group and the second group and the copolymer composed of the first group and the third group, and then mixing the copolymer separately. . Moreover, although the mixing ratio of each monomer is not specifically limited, When increasing the quantity of functional groups per unit polymer, what is necessary is just to increase the ratio of the monomer chosen from the said 2nd group and the 3rd group.

Although the total ion exchange capacity of a fluorine-containing copolymer is not specifically limited, It is preferable that it is 0.5-2.0 mg equivalent / g, and it is more preferable that it is 0.6-1.5 mg equivalent / g. Here, total ion exchange capacity means the equivalent of the exchanger per unit weight of dry resin, and can be measured by neutralization titration etc.

In the membrane main body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorine-containing polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorine-containing polymer having a carboxylic acid group are laminated. . By using this layer structure as the membrane main body 10, the selective permeability of cations such as sodium ions can be further improved.

In the case where the ion exchange membrane 1 is disposed in the electrolytic cell, the sulfonic acid layer 3 is usually disposed on the anode side of the electrolytic cell and the carboxylic acid layer 2 on the cathode side of the electrolytic cell.

It is preferable that the sulfonic acid layer 3 is comprised from the material with low electrical resistance, and it is preferable that a film thickness is thicker than the carboxylic acid layer 2 from a viewpoint of film strength. The film thickness of the sulfonic acid layer 3 becomes like this. Preferably it is 2-25 times of the carboxylic acid layer 2, More preferably, it is 3-15 times.

It is preferable that the carboxylic acid layer 2 has high anion exclusion property even if it is thin. Anion-exclusion here means the property which wants to interrupt the invasion and permeation | transmission of anion to the ion exchange membrane 1. In order to improve anion exclusion, disposing a carboxylic acid layer having a small ion exchange capacity with respect to the sulfonic acid layer is effective.

As the fluorine-containing polymer used for the sulfonic acid layer 3, for example, a polymer obtained by using CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F as the third group of monomers is suitable.

Carboxylic acids referred to as the fluorine-based polymer for use in sancheung (2) is, for example, as monomers of group 2 _{CF 2 = CFOCF 2 CF (CF} 2) O (CF 2) a polymer obtained by using ₂ COOCH ₃ are suitable.

(Coating layer)

The ion exchange membrane has a coating layer on at least one side of the membrane body. In addition, as shown in FIG. 23, in the ion exchange membrane 1, coating layers 11a and 11b are formed on both surfaces of the membrane body 10, respectively.

The coating layer includes inorganic particles and a binder.

As for the average particle diameter of an inorganic particle, it is more preferable that it is 0.90 micrometer or more. If the average particle diameter of the inorganic particles is 0.90 µm or more, the durability against impurities as well as gas adhesion is greatly improved. In other words, a particularly significant effect is obtained by increasing the average particle diameter of the inorganic particles and by satisfying the above-described specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by crushing gemstones can be used. Preferably, the inorganic particles obtained by gemstone grinding can be suitably used.

In addition, the average particle diameter of an inorganic particle can be 2 micrometers or less. If the average particle diameter of an inorganic particle is 2 micrometers or less, it can prevent that a film | membrane is damaged by an inorganic particle. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 µm.

Here, an average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation).

It is preferable that the shape of an inorganic particle is an irregular shape. Resistance to impurities is further improved. In addition, the particle size distribution of the inorganic particles is preferably wide.

It is preferable that an inorganic particle contains at least 1 sort (s) of inorganic substance chosen from the group which consists of an oxide of a group IV element of a periodic table, a nitride of a group IV element of a periodic table, and a carbide of a group IV element of a periodic table. More preferably, they are particles of zirconium oxide from the viewpoint of durability.

It is preferable that this inorganic particle is an inorganic particle manufactured by crushing the gemstone of an inorganic particle, or it is preferable to make spherical particle | grains of the uniform diameter of particle | grains into an inorganic particle by melting and refine | purifying the gemstone of an inorganic particle.

Examples of the raw material grinding method include, but are not particularly limited to, ball mills, bead mills, colloid mills, conical mills, disc mills, edge mills, milling mills, hammer mills, pellet mills, VSI mills, willy mills, roller mills, and jet mills. Etc. can be mentioned. Moreover, it is preferable to wash | clean after grinding | pulverization, and it is preferable to be acid-processed at that time. As a result, impurities such as iron adhering to the surface of the inorganic particles can be reduced.

The coating layer preferably comprises a binder. A binder is a component which keeps inorganic particle on the surface of an ion exchange membrane, and comprises a coating layer. It is preferable that a binder contains a fluorine-containing polymer from a viewpoint of resistance to electrolyte solution or the product by electrolysis.

As a binder, it is more preferable that it is a fluorine-containing polymer which has a carboxylic acid group or a sulfonic acid group from a tolerance with respect to the electrolyte solution and the product by electrolysis, and adhesiveness to the surface of an ion exchange membrane. When forming a coating layer on the layer (sulfonic acid layer) containing a fluorine-containing polymer which has a sulfonic acid group, it is more preferable to use the fluorine-containing polymer which has a sulfonic acid group as a binder of this coating layer. Moreover, when forming a coating layer on the layer (carboxylic acid layer) containing the fluorine-containing polymer which has a carboxylic acid group, it is more preferable to use the fluorine-containing polymer which has a carboxylic acid group as a binder of this coating layer.

It is preferable that it is 40-90 mass%, and, as for content of an inorganic particle in a coating layer, it is more preferable that it is 50-90 mass%. Moreover, it is preferable that it is 10-60 mass%, and, as for content of a binder, it is more preferable that it is 10-50 mass%.

The distribution density of the coating layer in the ion exchange membrane is preferably 0.05 to 2 mg per cm 2. In addition, when an ion exchange membrane has a concave-convex shape on the surface, it is preferable that the distribution density of a coating layer is 0.5-2 mg per cm <2>.

It does not specifically limit as a method of forming a coating layer, A well-known method can be used. For example, the method of apply | coating the coating liquid which disperse | distributed inorganic particle to the solution containing a binder by spray etc. is mentioned.

(Reinforced heartwood)

It is preferable that the ion exchange membrane has a reinforcing core material disposed inside the membrane body.

The reinforcing core is a member for enhancing the strength and dimensional stability of the ion exchange membrane. By arrange | positioning a reinforcing core material inside a membrane main body, especially expansion and contraction of an ion exchange membrane can be controlled to a desired range. Such an ion exchange membrane can maintain excellent dimensional stability for a long time without being stretched more than necessary in electrolysis or the like.

The configuration of the reinforcing core is not particularly limited, and may be formed by spinning a yarn called reinforcing yarn, for example. The reinforcement yarn mentioned here is a member which constitutes a reinforcing core material, which can impart desired dimensional stability and mechanical strength to the ion exchange membrane, and refers to a yarn that can stably exist in the ion exchange membrane. By using the reinforcing core material which radiated such reinforcement yarn, further excellent dimensional stability and mechanical strength can be provided to the ion exchange membrane.

The material of the reinforcing core material and the reinforcing yarn used for this is not particularly limited, but it is preferable that the material is resistant to acids, alkalis, or the like. desirable.

Examples of the fluorine-containing polymer used in the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether polymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetra Fluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, vinylidene fluoride polymer (PVDF), and the like. Among these, it is preferable to use the fiber which consists of polytetrafluoroethylene from a heat resistant and chemical resistant viewpoint especially.

The diameter of the reinforcing sand used for the reinforcing core is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The weave density (number of insertion lines per unit length) is preferably 5 to 50 lines / inch. The form of the reinforcing core is not particularly limited, and for example, a woven fabric, a nonwoven fabric, a knitted fabric, or the like is used, but it is preferably a form of a woven fabric. In addition, the thickness of the woven fabric is preferably 30 to 250 m, more preferably 30 to 150 m.

As the woven fabric or knitted fabric, monofilament, multifilament or yarns, slit yarns, and the like thereof can be used, and the weaving method can use various weaving methods such as plain weave, leno weave, knitting, cord weave, and seerker.

The weaving method and arrangement of the reinforcing core material in the membrane main body are not particularly limited and can be appropriately arranged in consideration of the size and shape of the ion exchange membrane, the desired physical properties and the use environment for the ion exchange membrane, and the like.

For example, the reinforcing core may be disposed along a predetermined direction of the membrane body, but from the viewpoint of dimensional stability, the reinforcing core is disposed along the predetermined first direction, and a second direction substantially perpendicular to the first direction is provided. Therefore, it is preferable to arrange a separate reinforcing core material. By arranging the plurality of reinforcing cores so as to run substantially straight inside the longitudinal membrane body of the membrane body, further superior dimensional stability and mechanical strength can be imparted in multiple directions. For example, an arrangement for weaving the reinforcing core material (warp) disposed along the longitudinal direction and the reinforcing core material (weft) arranged along the transverse direction on the surface of the membrane body is preferable. Lion weaved by inserting the same number of wefts into the weaving plain weave by twisting and inserting warp and weft alternately, or by weaving two warp and leno weaving by twisting two warp and two or several lines. It is more preferable to use a woven fabric (a loom) from the viewpoint of dimensional stability, mechanical strength, and ease of manufacture.

In particular, it is preferable that the reinforcing core is disposed along both directions of the MD direction (Machine Direction direction) and the TD direction (Transverse Direction direction) of the ion exchange membrane. That is, it is preferable to be woven in the MD direction and the TD direction. Here, MD direction means the direction (flow direction) in which a membrane main body and various core materials (for example, a reinforced core material, a reinforcement yarn, a sacrificial yarn etc. mentioned later) are conveyed in the manufacturing process of the ion exchange membrane mentioned later, and a TD direction is It refers to a direction approximately perpendicular to the MD direction. The yarn woven along the MD direction is called MD yarn, and the yarn woven along the TD direction is called TD yarn. Usually, the ion exchange membrane used for electrolysis is rectangular, and a longitudinal direction becomes MD direction, and the width direction becomes a TD direction in many cases. By weaving the reinforced MD core material and the reinforced TD core material, it is possible to give even more excellent dimensional stability and mechanical strength in multiple directions.

The spacing of the reinforcing cores is not particularly limited and can be appropriately arranged in consideration of desired physical properties, use environment, and the like for the ion exchange membrane.

The opening ratio of the reinforcing core material is not particularly limited, and is preferably 30% or more, more preferably 50% or more and 90% or less. The opening ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane.

The opening ratio of the reinforcing core is the total area (B) of the surface through which substances such as ions (electrolyte and cation (for example, sodium ions) contained) in the area (A) of either surface of the membrane body can pass. The ratio of (B / A). The total area (B) of the surface through which substances such as ions can pass can be referred to as the total area of the region where cations, electrolytes, and the like are not blocked by the reinforcing core included in the ion exchange membrane.

It is a schematic diagram for demonstrating the opening ratio of the reinforcing core material which comprises an ion exchange membrane. FIG. 24 enlarges a part of the ion exchange membrane and shows only the arrangement of the reinforcing core materials 21 and 22 in the region, and the illustration of the other members is omitted.

The total area C of the reinforcement core from the area A of the region including the area of the reinforcement core, which is also surrounded by the reinforcement core 21 arranged in the longitudinal direction and the reinforcement core 22 arranged in the horizontal direction. By subtracting, the total area B of the area through which substances such as ions in the area A of the area can pass can be obtained. That is, an opening ratio can be calculated | required by following formula (I).

Aperture ratio = (B) / (A) = ((A)-(C)) / (A). (I)

Among the reinforcing cores, a particularly preferable form is a tape yarn or a highly oriented monofilament containing PTFE in view of chemical resistance and heat resistance. Specifically, a high-strength porous sheet made of PTFE is a tape yarn slitted in tape form, or a 50 to 300 denier of a highly oriented monofilament made of PTFE, and a woven density of 10 to 50 lines / inch. It is more preferable that it is a reinforcement core material whose thickness is the range of 50-100 micrometers. It is more preferable that the opening ratio of the ion exchange membrane including such a reinforcing core material is 60% or more.

Examples of the shape of the reinforcing yarn include round yarns and tape-like yarns.

(Communication hole)

It is preferable that the ion exchange membrane has a communication hole inside the membrane main body.

The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, a communication hole is a tubular hole formed in the inside of a membrane main body, and is formed by eluting the sacrificial core material (or sacrificial thread) mentioned later. The shape and diameter of the communication hole can be controlled by selecting the shape and diameter of the sacrificial core material (sacrificial yarn).

By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured at the time of electrolysis. Although the shape of a communication hole is not specifically limited, According to the manufacturing method mentioned later, it can be set as the shape of the sacrificial core material used for formation of a communication hole.

The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With such a structure, in the part where the communication hole is formed in the cathode side of the reinforcing core material, ions (for example, sodium ions) transported through the electrolyte solution filled in the communication hole can also flow to the cathode side of the reinforcing core material. As a result, since the flow of cation is not blocked, the electrical resistance of the ion exchange membrane can be made lower.

The communication hole may be formed along only one predetermined direction of the membrane main body constituting the ion exchange membrane, but is formed in both the longitudinal direction and the transverse direction of the membrane main body in view of exhibiting more stable electrolytic performance. desirable.

[Production method]

As a suitable manufacturing method of an ion exchange membrane, the method of having the following (1) process-(6) process is mentioned.

(1) Process: The process of manufacturing the fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(2) Process: If necessary, a sacrificial yarn is disposed between adjacent reinforcing cores by at least weaving a plurality of reinforcing cores and a property of dissolving in an acid or alkali and forming at least a communication hole. To obtain the finished reinforcement.

(3) Process: The process of film-forming the said fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(4) Step: The step of embedding the reinforcing material in the film as necessary to obtain a membrane body having the reinforcing material disposed therein.

(5) Process: The process (hydrolysis process) of hydrolyzing the membrane main body obtained at process (4).

(6) Process: The process (coating process) of forming a coating layer in the film main body obtained at the process (5).

Hereinafter, each process is explained in full detail.

(1) Process: process for producing fluorine-containing polymer

In the step (1), the fluorine-containing polymer is produced by using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of a fluorine-containing polymer, in the manufacture of the fluorine-containing polymer which forms each layer, the mixing ratio of the monomer of a raw material may be adjusted.

(2) Process: manufacturing process of reinforcement

A reinforcing material is a woven fabric etc. which woven the reinforcement yarn. The reinforcing material is embedded in the film to form the reinforcing core material. When using an ion exchange membrane having communication holes, the sacrificial yarn is also woven into the reinforcing material. In this case, the blending amount of the sacrificial material is preferably 10 to 80 mass%, more preferably 30 to 70 mass% of the entire reinforcing material. By weaving a sacrificial thread, the mesh shift | offset of a reinforcement core material can also be prevented.

The sacrificial material has solubility in a film production process or an electrolytic environment, and rayon, polyethylene terephthalate (PET), cellulose, polyamide, and the like are used. Moreover, polyvinyl alcohol etc. which have a thickness of 20-50 denier and consist of monofilament or multifilament are also preferable.

In the step (2), by adjusting the arrangement of the reinforcing core material or the sacrificial material, the opening ratio, the arrangement of the communication holes, and the like can be controlled.

(3) process: filming process

In the step (3), the fluorine-containing polymer obtained in the step (1) is filmed using an extruder. A single layer structure may be sufficient as a film, and as above-mentioned, the two-layered structure of a sulfonic acid layer and a carboxylic acid layer may be sufficient, and the multilayered structure of three or more layers may be sufficient as it.

As a method of film-forming, the following are mentioned, for example.

A method of filming each of the fluorine-containing polymer having a carboxylic acid group and the fluorine-containing polymer having a sulfonic acid group separately.

A method in which a fluorine-containing polymer having a carboxylic acid group and a fluorine-containing polymer having a sulfonic acid group are co-extruded into a composite film.

In addition, a plurality of films may be sufficient respectively. Moreover, coextrusion of different kinds of films is preferable because it contributes to raising the adhesive strength of an interface.

(4) step: the step of obtaining the membrane body

In the step (4), the film body in which the reinforcing material is embedded is obtained by embedding the reinforcing material obtained in the step (2) inside the film obtained in the step (3).

As a preferable formation method of a film main body, (i) the fluorine-containing polymer which has a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) located in the cathode side (henceforth, the layer which consists of this is called a 1st layer), And forming a fluorine-containing polymer having a sulfonic acid group precursor (e.g., a sulfonylfluoride functional group) (hereinafter, referred to as a second layer) by a coextrusion method, and heating and vacuum source as necessary. Is laminated on a flat plate or drum having a large number of pores on the surface of the reinforcing material and the second layer / first layer composite film in the order of a reinforcing material and a heat-resistant release paper having air permeability. Integrating while removing air between each layer by decompression under temperature; (ii) Apart from the second layer / first layer composite film, the fluorine-containing polymer (third layer) having a sulfonic acid group precursor is previously filmed alone, and the surface is heated and heated using a vacuum source if necessary. The laminated film was laminated in the order of a composite film consisting of a third layer film, a reinforcing core material, and a second layer / first layer via a heat-resistant release paper having air permeability on a flat plate or a drum having a large number of pores thereon. The method of integrating, removing the air between each layer by pressure reduction under the temperature which melt | dissolves is mentioned.

Here, coextrusion of a 1st layer and a 2nd layer contributes to raising the adhesive strength of an interface.

Moreover, the method of integrating under reduced pressure has the feature that the thickness of the 3rd layer on a reinforcement material becomes large compared with the pressure press method. In addition, since the reinforcing material is fixed to the inner surface of the membrane main body, it has the performance of sufficiently maintaining the mechanical strength of the ion exchange membrane.

In addition, the variation of lamination described here is an example, and considering the desired layer structure, physical properties, etc. of a film body, a suitable lamination pattern (for example, the combination of each layer, etc.) can be selected, and then co-extruded.

Further, in order to further improve the electrical performance of the ion exchange membrane, a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is further interposed between the first layer and the second layer. It is also possible to use a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor instead of the layer.

The method for forming the fourth layer may be a method of separately preparing a fluorine-containing polymer having a carboxylic acid group precursor and a fluorine-containing polymer having a sulfonic acid group precursor, and then mixing the monomers with the carboxylic acid group precursor and the sulfonic acid group precursor. The method of copolymerizing the monomer which has the thing may be used.

In the case where the fourth layer is configured as an ion exchange membrane, the coextruded film of the first layer and the fourth layer is molded, and the third layer and the second layer are filmed independently of this, by the method described above. You may laminate | stack and three layers of a 1st layer / 4th layer / 2nd layer may be film-formed by coextrusion at once.

In this case, the direction in which the extruded film flows is the MD direction. In this way, a membrane body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material.

In addition, the ion exchange membrane preferably has a protruding portion, that is, a convex portion, made of a fluorine-containing polymer having a sulfonic acid group, on the surface side of the sulfonic acid layer. It does not specifically limit as a method of forming such a convex part, The well-known method of forming a convex part in the resin surface can be employ | adopted. Specifically, the method of embossing on the surface of a film main body is mentioned, for example. For example, when the said composite film, reinforcing material, etc. are integrated, the said convex part can be formed by using the release paper previously embossed. When forming a convex part by embossing, control of the height and placement density of a convex part can be performed by controlling the emboss shape (shape of a release paper) to be transferred.

(5) hydrolysis process

In the step (5), the membrane body obtained in the step (4) is hydrolyzed to convert the ion exchanger precursor into the ion exchanger (hydrolysis step).

In the step (5), the elution hole can be formed in the membrane main body by dissolving and removing the sacrificial yarn contained in the membrane main body with an acid or an alkali. In addition, the sacrificial yarn may remain in the communication hole without being completely dissolved and removed. In addition, the sacrificial yarn remaining in the communication hole may be dissolved and removed by the electrolytic solution when the ion exchange membrane is provided for electrolysis.

The sacrificial yarn is soluble in acid or alkali in the ion exchange membrane production process or in an electrolytic environment, and communication holes are formed in the site by dissolving the sacrificial material.

The step (5) can be performed by immersing the membrane body obtained in the step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (dimethyl sulfoxide) can be used.

It is preferable that the said mixed solution contains 2.5-4.0 N of KOH, and contains 25-35 mass% of DMSO.

As temperature of hydrolysis, it is preferable that it is 70-100 degreeC. The higher the temperature, the thicker the apparent thickness. More preferably, it is 75-100 degreeC.

It is preferable that it is 10 to 120 minutes as time of hydrolysis. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes.

Here, the process of forming a communication hole by eluting a sacrificial yarn is demonstrated in detail. 25 (a) and 25 (b) are schematic diagrams for explaining a method of forming communication holes of an ion exchange membrane.

In FIGS. 25A and 25B, only the communication holes 504 formed by the reinforcement yarns 52, the sacrificial yarns 504a, and the sacrificial yarns 504a are shown. The illustration is omitted.

First, the reinforcement yarn 52 which comprises a reinforcing core material in an ion exchange membrane, and the sacrificial yarn 504a for forming the communication hole 504 in an ion exchange membrane are used as a knitted reinforcement material. And the communication hole 504 is formed by eluting the sacrificial yarn 504a in the process (5).

According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a may be adjusted in accordance with the arrangement of the reinforcing core and the communication hole in the membrane main body of the ion exchange membrane.

In FIG. 25A, the reinforcement of the plain weave that woven the reinforcement yarn 52 and the sacrificial yarn 504a in both the longitudinal and transverse directions in the ground is illustrated. The arrangement of the 52 and the victim 504a can be changed.

(6) coating process

In the step (6), the coating layer can be formed by preparing a coating liquid containing the inorganic particles obtained by gemstone grinding or melting of the gemstone and a binder, and applying and drying the coating liquid on the surface of the ion exchange membrane obtained in the step (5). .

As a binder, after hydrolyzing the fluorine-containing polymer having an ion exchange group precursor with an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH), it is immersed in hydrochloric acid to replace the counter ion of the ion exchange group with H ⁺ . One binder (eg, a fluorine-containing polymer having a carboxyl or sulfo group) is preferred. Since it becomes easy to melt | dissolve in water and ethanol mentioned later by this, it is preferable.

This binder is dissolved in a solution in which water and ethanol are mixed. Moreover, the preferable volume ratio of water and ethanol is 10: 1-1:10, More preferably, it is 5: 1-1: 5, More preferably, it is 2: 1-1: 2. In the solution thus obtained, the inorganic particles are dispersed by a ball mill to obtain a coating solution. At this time, the average particle diameter of a particle | grains, etc. can also be adjusted by adjusting the time and the rotation speed at the time of dispersion. In addition, the preferable compounding quantity of an inorganic particle and a binder is as above-mentioned.

The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, but is preferably a light coating liquid. Thereby, it becomes possible to apply | coat uniformly to the surface of an ion exchange membrane.

In addition, when dispersing the inorganic particles, a surfactant may be added to the dispersion. As surfactant, a nonionic surfactant is preferable, For example, HS-210, NS-210, P-210, E-212 by Nichi-yu Corporation, etc. are mentioned.

An ion exchange membrane is obtained by apply | coating the obtained coating liquid to the surface of an ion exchange membrane by spray coating or roll coating.

[Microporous membrane]

As described above, the microporous membrane of the present embodiment is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various microporous membranes can be applied.

Although the porosity of the microporous membrane of this embodiment is not specifically limited, For example, it can be 20-90, Preferably it is 30-85. The porosity can be calculated by the following formula, for example.

Porosity = (1- (Dry Film Weight in Dry State) / (Volume calculated from the thickness, width and length of the film and weight calculated from the density of the film material)) × 100

Although the average pore diameter of the microporous membrane of this embodiment is not specifically limited, For example, it can be 0.01 micrometer-10 micrometers, Preferably it is 0.05 micrometer-5 micrometers. The average pore diameter is, for example, the film is vertically cut in the thickness direction, and the cut surface is observed by FE-SEM. It can obtain | require by measuring and averaging about 100 points of the diameter of the hole observed.

Although the thickness of the microporous film of this embodiment is not specifically limited, For example, it can be 10 micrometers-1000 micrometers, Preferably it is 50 micrometers-600 micrometers. The said thickness can be measured using a micrometer (made by Mitsutoyo Corporation) etc., for example.

Specific examples of the microporous membranes described above include Agir's Zirfon Perl UTP 500 (also referred to as Zirfon membrane in this embodiment), International Publication No. 2013-183584, International Publication No. 2016-203701, etc. The things described are mentioned.

The reason why the laminated body with the diaphragm of this embodiment expresses the outstanding electrolytic performance is estimated as follows. In the case where the prior art membrane and the electrode are firmly bonded by a method such as thermocompression bonding, the electrode is in a state of being embedded in the membrane and is physically bonded. This adhesive portion prevents the movement of sodium ions in the film, and the voltage is greatly increased. On the other hand, by contacting the electrolytic electrode with a diaphragm or a feeder with an appropriate adhesive force as in the present embodiment, the movement of sodium ions, which has been a problem in the prior art, is prevented. Thereby, when the diaphragm or feeder and the electrode for electrolysis are in contact with moderate adhesive force, it is possible to express the outstanding electrolytic performance, being an integral body of a diaphragm or feeder and an electrode for electrolysis.

[Winding body]

The wound body of this embodiment includes the laminated body of this embodiment. That is, the wound body of this embodiment is a thing formed by winding the laminated body of this embodiment. Like the winding body of this embodiment, handling property can be improved further by winding up and downsizing the laminated body of this embodiment.

[Electrolysis tank]

The electrolytic cell of this embodiment contains the laminated body of this embodiment. EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of an electrolytic cell is explained in full detail, for example, when salt electrolysis is performed using an ion exchange membrane as a diaphragm.

[Electrolysis cell]

26 is a cross-sectional view of the electrolytic cell 1.

The electrolytic cell 1 includes the anode chamber 10, the cathode chamber 20, the partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, and the anode provided in the anode chamber 10. 11 and a cathode 21 provided in the cathode chamber 20. If necessary, the base 18a and the reverse current absorbing layer 18b formed on the base 18a may be provided, and the reverse current absorber 18 provided in the cathode chamber may be provided. The positive electrode 11 and the negative electrode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 has the following cathode structure. The negative electrode structure 40 includes a negative electrode chamber 20, a negative electrode 21 provided in the negative electrode chamber 20, and a reverse current absorber 18 provided in the negative electrode chamber 20, and the reverse current absorber 18. 30 has a base 18a and a reverse current absorbing layer 18b formed on the base 18a, and the cathode 21 and the reverse current absorbing layer 18b are electrically connected to each other. The negative electrode chamber 20 further includes a current collector 23, a support 24 supporting the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the electrical power collector 23 and the negative electrode 21. The support body 24 is provided between the collector 23 and the partition 30. The current collector 23 is electrically connected to the negative electrode 21 via the metal elastic body 22. The partition 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition 30, the support body 24, the collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected to each other. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be connected indirectly via a current collector, a support, a metal elastic body, a partition, or the like. It is preferable that the whole surface of the cathode 21 is covered with a catalyst layer for the reduction reaction. In addition, in the form of electrical connection, the partition 30 and the support body 24, the support body 24 and the collector 23, the collector 23 and the metal elastic body 22 are respectively directly attached, and the metal elastic body 22 ) May be laminated on the cathode 21. Welding etc. are mentioned as a method of attaching these structural members directly to each other. In addition, the reverse current absorber 18, the negative electrode 21, and the current collector 23 may be collectively referred to as the negative electrode structure 40.

FIG. 27 is a cross-sectional view of two electrolytic cells 1 adjacent in the electrolytic cell 4. 28 shows the electrolytic cell 4. 29 shows a step of assembling the electrolytic cell 4. As shown in FIG. 27, the electrolytic cell 1, the cation exchange membrane 2, and the electrolytic cell 1 are arranged in series in this order. The ion exchange membrane 2 is arrange | positioned between the anode chamber of one electrolytic cell 1 and the cathode chamber of the other electrolytic cell 1 among two electrolytic cells which adjoin in an electrolytic cell. In other words, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are spaced apart by the cation exchange membrane 2. As shown in FIG. 28, the electrolytic cell 4 is composed of a plurality of electrolytic cells 1 connected in series via an ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 29, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series via an ion exchange membrane 2 and being connected by a press 5.

The electrolytic cell 4 has the positive terminal 7 and the negative terminal 6 connected to a power supply. The positive electrode 11 of the electrolytic cell 1 positioned at the shortest of the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4 is electrically connected to the positive electrode terminal 7. Among the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4, the negative electrode 21 of the electrolytic cell located at the end opposite to the positive electrode terminal 7 is electrically connected to the negative electrode terminal 6. The electric current at the time of electrolysis flows toward the negative electrode terminal 6 from the positive terminal 7 side via the positive electrode and the negative electrode of each electrolytic cell 1. Moreover, you may arrange | position the electrolytic cell (anode terminal cell) which has only an anode chamber, and the electrolytic cell (cathode terminal cell) which has only a cathode chamber in the both ends of the electrolytic cell 1 which connected. In this case, the positive terminal 7 is connected to the positive terminal cell disposed at one end thereof, and the negative terminal 6 is connected to the negative terminal cell arranged at the other end thereof.

In the case of electrolysis of brine, brine is supplied to each anode chamber 10, and pure or low concentration aqueous sodium hydroxide solution is supplied to the cathode chamber 20. Each liquid is supplied to each electrolytic cell 1 from electrolyte supply pipe (not shown) via electrolyte supply hose (not shown). In addition, electrolyte solution and the product by electrolysis are collect | recovered from an electrolyte collection pipe (not shown). In electrolysis, sodium ions in brine move from the anode chamber 10 of one electrolytic cell 1 through the ion exchange membrane 2 to the cathode chamber 20 of the neighboring electrolytic cell 1. Therefore, the current during electrolysis flows along the direction in which the electrolytic cells 1 are connected in series. That is, the current flows from the anode chamber 10 toward the cathode chamber 20 via the cation exchange membrane 2. By electrolysis of the brine, chlorine gas is produced on the anode 11 side, and sodium hydroxide (solute) and hydrogen gas are produced on the cathode 21 side.

(Positive room)

The anode chamber 10 includes a cathode 11 or an anode feeder 11. When the electrode for electrolysis of this embodiment is inserted in the anode side, 11 functions as a positive electrode feeder. When the electrode for electrolysis of this embodiment is not inserted in the anode side, 11 functions as an anode. In addition, the anode chamber 10 is disposed on an anode side electrolyte supply portion for supplying an electrolyte solution to the anode chamber 10 and an anode side electrolyte supply portion, and a baffle plate disposed to be substantially parallel or oblique with the partition wall 30. And it is preferable to have an anode side gas-liquid separation part arrange | positioned above the baffle plate and isolate | separates a gas from the electrolyte solution which gas mixed.

(anode)

When the electrode for electrolysis of this embodiment is not inserted in the anode side, the anode 11 is provided in the frame of the anode chamber 10. As the anode 11, a metal electrode such as so-called DSA (registered trademark) can be used. DSA is a titanium-based electrode whose surface was covered with an oxide containing ruthenium, iridium and titanium.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Positive electrode feeder)

When the electrode for electrolysis of this embodiment is inserted in the anode side, the positive electrode feeder 11 is provided in the frame of the anode chamber 10. As the positive electrode feeder 11, a metal electrode such as DSA (registered trademark) or the like may be used, or titanium without a catalyst coating may be used. It is also possible to use DSA with a thinner catalyst coating thickness. Moreover, the used anode can also be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Anode-side electrolyte supply unit)

The anode-side electrolyte supply unit supplies the electrolyte solution to the anode chamber 10 and is connected to the electrolyte solution supply pipe. It is preferable that an anode side electrolyte supply part is arrange | positioned under the anode chamber 10. As an anode side electrolyte supply part, the pipe (dispersion pipe) etc. which have an opening part formed in the surface can be used, for example. It is more preferable that such a pipe is arrange | positioned in parallel with the bottom part 19 of an electrolysis cell along the surface of the anode 11. This pipe is connected to the electrolyte supply pipe (liquid supply nozzle) which supplies electrolyte solution in the electrolysis cell 1. The electrolyte solution supplied from the liquid supply nozzle is conveyed to the electrolysis cell 1 by the pipe, and is supplied to the inside of the anode chamber 10 from the opening provided in the surface of the pipe. By arranging the pipes parallel to the bottom portion 19 of the electrolytic cell along the surface of the anode 11, the electrolyte can be uniformly supplied into the anode chamber 10, which is preferable.

(Positive side gas-liquid separator)

It is preferable that the anode-side gas-liquid separator is disposed above the baffle plate. During electrolysis, the anode-side gas-liquid separator has a function of separating the generated gas such as chlorine gas and the electrolyte. In addition, unless otherwise indicated, an upper side means the upward direction in the electrolysis cell 1 of FIG. 26, and a lower side means the downward direction in the electrolysis cell 1 of FIG.

At the time of electrolysis, when the generated gas and electrolyte generated in the electrolytic cell 1 become mixed phase (gas-liquid mixed phase) and discharged out of the system, vibration occurs due to pressure fluctuation inside the electrolytic cell 1, and physical damage of the ion exchange membrane is prevented. I may cause it. In order to suppress this, it is preferable that the positive electrode side gas-liquid separation part for separating a gas and a liquid is provided in the electrolysis cell 1 of this embodiment. It is preferable that a defoaming plate for removing bubbles is provided in the anode-side gas-liquid separator. When a gas-liquid mixture flows through a vesicle plate, a bubble bursts and can be isolate | separated into electrolyte solution and gas. As a result, vibration during electrolysis can be prevented.

(Baffle version)

It is preferable that the baffle plate is disposed above the anode-side electrolyte supply portion, and is disposed substantially parallel to or inclined with the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. By providing the baffle plate, the electrolyte solution (salt water, etc.) can be circulated internally in the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged to be spaced apart from the space near the anode 11 and the space near the partition wall 30. From this viewpoint, the baffle plate is preferably provided so as to face each surface of the anode 11 and the partition wall 30. In the space near the anode partitioned by the baffle plate, electrolytic solution concentration (saline concentration) decreases as electrolysis proceeds, and product gas such as chlorine gas is generated. Thereby, the specific gravity difference of gas-liquid arises in the space near the anode 11 divided by the baffle plate, and the space near the partition 30. As shown in FIG. By using this, the internal circulation of the electrolyte solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolyte solution in the anode chamber 10 can be made more uniform.

Although not shown in FIG. 26, a current collector may be separately provided inside the anode chamber 10. As such an electrical power collector, it can also be set as the material and structure similar to the electrical power collector of the negative electrode chamber mentioned later. In the anode chamber 10, the anode 11 itself can also function as a current collector.

(septum)

The partition 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition 30 may be called a separator and divides the anode chamber 10 and the cathode chamber 20. As the partition 30, a well-known thing can be used as a separator for electrolysis, For example, the partition which welded the plate which consists of nickel to the cathode side, and titanium to the anode side, etc. are mentioned.

(Cathode room)

The negative electrode chamber 20 functions as a negative electrode feeder when the electrolytic electrode of the present embodiment is inserted into the negative electrode side, and 21 when the electrolytic electrode of the present embodiment is not inserted into the negative electrode side. Functions as a cathode. When the reverse current absorber is provided, the negative electrode or the negative electrode feeder 21 and the reverse current absorber are electrically connected to each other. In addition, it is preferable that the cathode chamber 20 also has a cathode side electrolyte solution supply section and a cathode side gas-liquid separation section similarly to the anode chamber 10. In addition, description is abbreviate | omitted about the same thing as each part which comprises the anode chamber 10 among each site | part which comprises the cathode chamber 20. As shown in FIG.

(cathode)

When the electrode for electrolysis of this embodiment is not inserted in the cathode side, the cathode 21 is provided in the frame of the cathode chamber 20. It is preferable that the negative electrode 21 has a catalyst layer which covers a nickel substrate and a nickel substrate. As a component of the catalyst layer on the nickel substrate, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd , Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho And metals such as Er, Tm, Yb and Lu, and oxides or hydroxides of the metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may give reduction process to the negative electrode 21 as needed. As the base material of the negative electrode 21, one in which nickel, nickel alloy, iron, or stainless steel is plated with nickel may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Cathode feeder)

When the electrode for electrolysis of this embodiment is inserted in the cathode side, the cathode feeder 21 is provided in the frame of the cathode chamber 20. The catalyst component may be coated on the negative electrode feeder 21. The catalyst component may be originally used as a negative electrode and remain. As components of the catalyst layer, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Metals, such as Tm, Yb, Lu, and the oxide or hydroxide of this metal are mentioned. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may use what plated nickel with nickel, nickel alloys, iron, or stainless steel which are not catalyst coated. As the base material of the negative electrode feeder 21, a plated nickel on nickel, a nickel alloy, iron or stainless may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

Reverse Current Absorption Layer

A material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected as the material of the reverse current absorbing layer. For example, nickel, iron, etc. are mentioned.

(Current collector)

The negative electrode chamber 20 preferably includes a current collector 23. This increases the current collecting effect. In the present embodiment, the current collector 23 is a porous plate, and is preferably disposed substantially parallel to the surface of the negative electrode 21.

The current collector 23 is preferably made of an electrically conductive metal such as nickel, iron, copper, silver, titanium, or the like. The current collector 23 may be a mixture of these metals, an alloy or a composite oxide. In addition, as long as it is a shape which functions as an electrical power collector, the shape of the electrical power collector 23 may be any shape, and plate-shaped or network-shaped may be sufficient as it.

(Metal elastomer)

By providing the metal elastic body 22 between the collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, The distance between each anode 11 and each cathode 21 can be shortened, and the voltage applied to the entire plurality of electrolytic cells 1 connected in series can be lowered. By lowering the voltage, the total consumption can be reduced. Moreover, when the metal elastic body 22 is provided and the laminated body containing the electrode for electrolysis which concerns on this embodiment is installed in an electrolytic cell, the said electrode for electrolysis by the pressure pressed by the metal elastic body 22 is carried out. Can be kept in a stable position.

As the metallic elastic body 22, a spring member, such as a spiral spring and a coil, a cushion mat, etc. can be used. As the metal elastic body 22, a suitable one can be appropriately adopted in consideration of a stress or the like which presses the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the collector 23 on the cathode chamber 20 side, or may be provided on the surface of the partition wall on the anode chamber 10 side. Usually, since both chambers are partitioned so that the cathode chamber 20 becomes smaller than the anode chamber 10, from the viewpoint of the strength of the frame or the like, the metal elastic body 22 is used for the current collector 23 of the cathode chamber 20. It is preferable to provide between and the cathode 21. Moreover, it is preferable that the metal elastic body 22 consists of metal which has electrical conductivity, such as nickel, iron, copper, silver, titanium.

(Support)

The negative electrode chamber 20 preferably includes a support 24 for electrically connecting the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently.

The support 24 is preferably made of a metal having electrical conductivity such as nickel, iron, copper, silver, titanium, or the like. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod, plate, or network. The support body 24 is plate-shaped, for example. The plurality of supports 24 are disposed between the partition wall 30 and the current collector 23. The plurality of supports 24 are arranged such that their respective surfaces are parallel to each other. The support body 24 is disposed substantially perpendicular to the partition wall 30 and the current collector 23.

(Anode side gasket, cathode side gasket)

It is preferable that the anode side gasket is arranged on the surface of the frame body constituting the anode chamber 10. It is preferable that the cathode side gasket is arrange | positioned at the surface of the frame body which comprises the cathode chamber 20. As shown in FIG. The anode side gasket of one electrolytic cell and the cathode side gasket of the electrolytic cell adjacent to this are connected so that the electrolytic cells may be clamped so that the ion exchange membrane 2 may be pinched (refer FIG. 26, 27). By these gaskets, when connecting a plurality of electrolytic cells 1 in series via the ion exchange membrane 2, airtightness can be provided to a connection location.

A gasket seals between an ion exchange membrane and an electrolysis cell. As a specific example of a gasket, a frame-shaped rubber sheet etc. in which the opening part was formed in the center are mentioned. The gasket is required to be resistant to corrosive electrolytes, generated gases and the like and to be used for a long time. Therefore, from the viewpoint of chemical resistance and hardness, vulcanized products, peroxide crosslinked products and the like of ethylene propylene diene rubber (EPDM rubber) and ethylene propylene rubber (EPM rubber) are usually used as the gasket. Moreover, the gasket which coat | covered the area | region (contact part) which contact | connects a liquid as needed with fluororesin, such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether polymer (PFA), can also be used. These gaskets should just have opening parts, respectively, so that the flow of electrolyte solution may not be disturbed, The shape is not specifically limited. For example, a frame-shaped gasket is bonded with an adhesive or the like along the circumferential edge of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20. For example, when connecting two electrolytic cells 1 via the ion exchange membrane 2 (refer FIG. 27), when each electrolytic cell 1 which bonded the gasket through the ion exchange membrane 2 is fastened, do. Thereby, it can suppress that an electrolyte solution, the alkali metal hydroxide produced by electrolysis, chlorine gas, hydrogen gas, etc. leak to the exterior of the electrolysis cell 1.

(Ion exchange membrane)

As the ion exchange membrane 2, it is as described in the term of the said ion exchange membrane.

(Hydraulic)

In the electrolytic cell of this embodiment, the electrolytic cell in the case of performing electrolytic electrolysis has the structure which changed the ion exchange membrane in the electrolytic cell in the case of performing the above-mentioned salt electrolysis to a microporous membrane. In addition, since the raw material to be supplied is water, it differs from the electrolytic cell in the case of performing the above-mentioned salt electrolysis. As for other configurations, the same configuration as the electrolytic cell in the case of performing salt electrolysis can also be adopted. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. However, in the case of hydrolysis, since oxygen gas is only generated in the anode chamber, the same material as the cathode chamber is used. Can be used. For example, nickel etc. can be mentioned. In addition, the anode coating is suitably a catalyst coating for oxygen generation. Examples of catalyst coatings include metals, oxides, hydroxides, and the like of platinum group metals and transition metals. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used.

(Use of Laminate)

As mentioned above, the laminated body of this embodiment can improve the work efficiency at the time of electrode update in an electrolytic cell, and can express the outstanding electrolytic performance after an update. In other words, the laminated body of this embodiment can be used suitably as a laminated body for member exchange of an electrolytic cell. In addition, the laminated body at the time of applying to such a use is called especially "membrane electrode assembly."

(Packaging)

It is preferable that the laminated body of this embodiment conveys etc. in the state enclosed in the packaging material. That is, the package of this embodiment is provided with the laminated body of this embodiment, and the packaging material which wraps the said laminated body. Since the package of this embodiment is comprised as mentioned above, the adhesion and damage of the contamination which may arise when carrying the laminated body of this embodiment can be prevented. In the case of using the electrolytic cell for exchanging the member, it is particularly preferable to carry or the like as the package of the present embodiment. It does not specifically limit as a packaging material in this embodiment, Various well-known packaging materials can be applied. In addition, the package of this embodiment is not limited to the following, For example, it can manufacture by the method of packaging a laminated body of this embodiment with the packaging material of a clean state, and then encapsulating.

Third Embodiment

Here, the third embodiment of the present invention will be described in detail with reference to FIGS. 43 to 62.

[Laminated body]

The laminate of the third embodiment (hereinafter, simply referred to as "the present embodiment" in the term of <third embodiment>) includes at least one region (hereinafter, simply "fixed region") of the diaphragm and the surface of the diaphragm. And a proportion of the region on the surface of the diaphragm, wherein the proportion of the region on the surface of the diaphragm is greater than 0% and less than 93%. Since it is comprised in this way, the laminated body of this embodiment can improve the work efficiency at the time of electrode update in an electrolytic cell, and can express the outstanding electrolytic performance after an update.

That is, with the laminated body of this embodiment, when updating an electrode, an electrode can be updated by the simple operation similar to the update of a diaphragm, without involving complicated operations, such as peeling the existing electrode fixed to the electrolysis cell. Therefore, the work efficiency is greatly improved.

Moreover, according to the laminated body of this embodiment, the electrolytic performance of the existing electrolytic cell can be maintained or improved equivalent to the performance at the time of a new article. Therefore, the electrode fixed to the existing electrolytic cell and functioning as an anode and a cathode only needs to function as a feeder, and it is possible to significantly reduce or zero the catalyst coating. The feeder as used herein means a deteriorated electrode (ie, an existing electrode), an electrode not coated with a catalyst, or the like.

[Electrode Electrode]

Although the electrode for electrolysis in this embodiment is not specifically limited as long as it is an electrode used for electrolysis, It is preferable that the area (corresponding to area S2 of the conduction surface mentioned later) of the surface facing the diaphragm of an electrode for electrolysis is 0.01 m <2> or more. Do. "An opposing surface with a diaphragm" means the surface of the side in which a diaphragm exists among the surfaces which an electrode for electrolysis has. That is, the opposing surface with the diaphragm in an electrolytic electrode can also be called the surface which contact | connects the surface of a diaphragm. When the area of the facing surface with the said diaphragm in an electrolytic electrode is 0.01 m <2> or more, sufficient productivity can be ensured, and especially there exists a tendency which can obtain sufficient productivity in performing industrial electrolysis. Thus, from the viewpoint of ensuring sufficient productivity and practicality as a laminate to be used for updating the electrolytic cell, the area of the opposing face of the diaphragm in the electrolytic electrode is more preferably 0.1 m 2 or more, 1 More than m <2> is more preferable. Such an area can be measured by the method described in an Example, for example.

The electrode for electrolysis in this embodiment can obtain favorable handling property, and is a unit from a viewpoint of having favorable adhesive force, such as a diaphragm, such as an ion exchange membrane and a microporous membrane, a feeder (a deteriorated electrode and a catalyst uncoated electrode), etc. The force applied per mass and unit area is preferably 1.6 N / (mg · cm 2) or less, more preferably less than 1.6 N / (mg · cm 2), still more preferably less than 1.5 N / (mg · cm 2) More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred.

From the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and even more preferably 0.1 N / mg · cm 2 or more. More preferably, it is 0.14 N / (mg * cm <2>) or more. 0.2 N / (mg * cm <2>) or more is more preferable from a viewpoint of the ease of handling in a large size (e.g., size 1.5 m x 2.5 m).

The said applied force can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, arithmetic mean surface roughness, etc., for example. More specifically, for example, when the porosity is increased, the applied force tends to be small, and when the porosity is decreased, the applied force tends to be large.

In addition, good handling properties can be obtained, good adhesion to diaphragms such as ion exchange membranes and microporous membranes, deteriorated electrodes, catalyst uncoated feeders and the like, and from the viewpoint of economy, the mass per unit area is 48 mg / cm 2 or less. It is preferable, More preferably, it is 30 mg / cm <2> or less, More preferably, it is 20 mg / cm <2> or less and 15 mg / cm <2> or less from a comprehensive viewpoint which combined handling property, adhesiveness, and economics. The lower limit is not particularly limited, but is, for example, about 1 mg / cm 2.

The said mass per unit area can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, etc., for example. More specifically, for example, if the thickness is the same, the mass per unit area tends to be smaller when the porosity is increased, and the mass per unit area tends to be larger when the porosity is reduced.

The force applied can be measured by the following method (i) or (ii), the value obtained by the measurement of the method (i) (also called "the applied force (1)"), and the method (ii) Although the value obtained by the measurement of (it may also be called "the applied force 2") may be same or different, it is preferable that either value is less than 1.5 N / mg * cm <2>.

[Method (i)]

Nickel plate obtained by blasting with alumina of particle number 320 (thickness 1.2 mm, width 200 mm) and an ion exchange membrane coated with inorganic particles and a binder on both sides of a membrane of a perfluorocarbon polymer into which an ion exchanger was introduced (horizontal 170 mm long) and an electrode sample (130 mm wide) are laminated | stacked in this order, this laminated body is fully immersed in pure water, and a sample for a measurement is obtained by removing the excess moisture adhering to the laminated body surface. In addition, the arithmetic mean surface roughness Ra of the nickel plate after a blasting process is 0.5-0.8 micrometer. The specific calculation method of arithmetic mean surface roughness Ra is as having described in the Example.

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were raised in 10 mm in the vertical direction. Measure the weight when This measurement is performed three times to calculate an average value.

The average value is divided by the area of the overlapped portion of the electrode sample and the ion exchange membrane and the mass of the electrode sample of the overlapped portion with the ion exchange membrane, and the force applied per unit mass and unit area (1) (N / mg · cm 2) To calculate.

The force (1) applied per unit mass and unit area obtained by the method (i) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is preferable that it is 1.6 N / (mg * cm <2>) or less from a viewpoint of having more, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more and more preferably 0.14 N / (mg · cm 2) and 0.2 N / (mg · cm 2) from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m). ) Is more preferable.

[Method (ii)]

The nickel plate (thickness 1.2 mm, width 200 mm, the same nickel plate as the method (i)) and the electrode sample (length 130 mm) obtained by blasting with alumina of particle number 320 were laminated in this order. After fully immersing the laminate with pure water, a sample for measurement is obtained by removing excess moisture adhering to the laminate surface. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were 10 mm in the vertical direction. The weight at the time of rise is measured. This measurement is performed three times to calculate an average value.

This average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate, and the mass of the electrode sample in the overlapped portion of the nickel plate, and the adhesive force 2 per unit mass and unit area (N / mg · cm 2) is obtained. Calculate.

The force (2) applied per unit mass and unit area obtained by the method (ii) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is preferable that it is 1.6 N / (mg * cm <2>) or less from a viewpoint of having more, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more, and even more preferably, from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m), still more preferably 0.14 N / (mg · cm 2) or more.

It is preferable that the electrolytic electrode in this embodiment contains an electrolytic electrode base material and a catalyst layer. Although the thickness (gauge thickness) of the said electrolytic electrode base material is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feedstock), and an electrode without a catalyst coating (grade 300 micrometers or less are preferable from a viewpoint of having a good adhesive force with the whole), and being rolled suitably, being able to bend it favorably, and facilitating handling in a large size (e.g., size 1.5 m x 2.5 m). 205 micrometers or less are more preferable, 155 micrometers or less are more preferable, 135 micrometers or less are still more preferable, 125 micrometers or less are still more preferable, 120 micrometers or less are still more preferable, 100 micrometers or less are further more preferable In addition, from a viewpoint of handling property and economical efficiency, 50 micrometers or less are further more preferable. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), From the viewpoint of having good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and also in a large size (e.g., size 1.5 m x 2.5 m). It is more preferable that it is 95% or more from the viewpoint of easy handling. The upper limit is 100%.

[Method (2)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the condition of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 280 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), It is preferable that it is 75% or more, and it is more preferable that it is 80% or more from the viewpoint of having favorable adhesive force, and being able to wind up in roll shape suitably, and bend | bending favorably. It is more preferable that it is 90% or more from a viewpoint that handling at a size (for example, size 1.5 m x 2.5 m) becomes easy. The upper limit is 100%.

[Method (3)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 145 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), It is preferable that it has a favorable adhesive force and is a porous structure from a viewpoint of the prevention of the residence of the gas which arises during electrolysis, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80% or less, still more preferably 20 to 75%.

In addition, an opening ratio is a ratio of an opening part per unit volume. The calculation method varies depending on whether the opening is also considered to submicron order or only the visible opening. In this embodiment, the volume V was calculated from the values of the gauge thickness, the width, and the length of the electrode, and the weight W was measured, and the porosity A was calculated by the following formula.

A = (1- (W / (V × ρ)) × 100

ρ is the density (g / cm 3) of the material of the electrode. For example, nickel is 8.908 g / cm 3 and titanium is 4.506 g / cm 3. The adjustment of the porosity is to change the area punching the metal per unit area if the punching metal, change the SW (short diameter), LW (long diameter), the feeding value if the expanded metal, the mesh diameter of the metal fiber, By changing the number of meshes, changing the pattern of the photoresist to be used for electroforming, changing the metal fiber diameter and fiber density for nonwoven fabrics, and changing the mold for forming the voids for the foamed metal, etc. Adjust

EMBODIMENT OF THE INVENTION Hereinafter, one form of the electrode for electrolysis in this embodiment is demonstrated.

It is preferable that the electrolytic electrode which concerns on this embodiment contains an electrolytic electrode base material and a catalyst layer. The catalyst layer may be composed of a plurality of layers as described below or may have a single layer structure.

As illustrated in FIG. 43, the electrolytic electrode 100 according to the present embodiment includes a pair of first layers 20 covering both surfaces of the electrolytic electrode substrate 10 and the electrolytic electrode substrate 10. It is provided. It is preferable that the 1st layer 20 coat | covers the electrolytic electrode base material 10 whole. As a result, the catalytic activity and durability of the electrode for electrolysis tends to be improved. In addition, the first layer 20 may be laminated only on one surface of the electrode base 10 for electrolysis.

In addition, as shown in FIG. 43, the surface of the first layer 20 may be covered with the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, only one surface of the first layer 20 may be laminated on the second layer 30.

(Electrode base for electrolysis)

The electrolytic electrode substrate 10 is not particularly limited, but a valve metal such as nickel, nickel alloy, stainless steel or titanium may be used, and at least one selected from nickel (Ni) and titanium (Ti) may be used. It is preferable to include the element of a species.

When stainless steel is used in a high concentration aqueous alkali solution, considering that iron and chromium are eluted, and that the electrical conductivity of stainless steel is about 1/10 of nickel, the electrolytic electrode substrate includes nickel (Ni). The substrate is preferred.

In addition, when the electrolytic electrode base material 10 is used in the chlorine gas generation | occurence atmosphere in the high concentration saline solution near saturation, it is preferable that a material is titanium with high corrosion resistance.

There is no restriction | limiting in particular in the shape of the electrode base material 10 for electrolysis, An appropriate shape can be selected according to the objective. As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used. Especially, a punching metal or an expanded metal is preferable. In addition, electroforming is a technique which manufactures a metal thin film of a precise pattern by combining photolithography and an electroplating method. It is a method of pattern-forming with a photoresist on a board | substrate, electroplating to the part which is not protected by a resist, and obtaining metal foil.

The shape of the electrode base material for electrolysis has suitable specifications depending on the distance between the anode and the cathode in the electrolytic cell. Although not particularly limited, in the case where the anode and the cathode have a finite distance, an expanded metal or a punched metal shape can be used, and in the case of a so-called zero gap electrolytic cell in which the ion exchange membrane and the electrode are in contact, a woven mesh woven with fine lines , Wire mesh, foamed metal, metal nonwoven fabric, expanded metal, punched metal, metal porous foil and the like can be used.

Examples of the electrode base 10 for electrolysis include a metal porous foil, a wire mesh, a metal nonwoven fabric, a punching metal, an expanded metal or a foamed metal.

As a board | plate material before processing with a punching metal and an expanded metal, the board | plate material roll-molded, electrolytic foil, etc. are preferable. It is preferable that the electrolytic foil is further plated with the same element as the base material as post-treatment to form irregularities on one or both surfaces.

In addition, it is preferable that the thickness of the electrolytic electrode base material 10 is 300 micrometers or less as mentioned above, It is more preferable that it is 205 micrometers or less, It is more preferable that it is 155 micrometers or less, It is further more preferable that it is 135 micrometers or less, 125 It is still more preferable that it is micrometer or less, It is still more preferable that it is 120 micrometers or less, It is still more preferable that it is 100 micrometers or less, It is further more preferable that it is 50 micrometers or less from a viewpoint of handling property and economy. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In the electrode base for electrolysis, it is preferable to relieve the residual stress at the time of processing by annealing the electrode base for electrolysis in an oxidizing atmosphere. Moreover, in order to improve the adhesiveness with the catalyst layer coat | covered with the said surface, the surface of an electrolytic electrode base material uses unevenness | corrugation using a steel grid, alumina powder, etc., and it is preferable to increase a surface area by acid treatment after that. Do. Or it is preferable to plating by the same element as a base material, and to increase a surface area.

In order to make the surface of the 1st layer 20 and the electrode base material 10 for electrolysis adhere to the electrode base material 10 for electrolysis, it is preferable to perform the process which increases a surface area. Examples of the treatment for increasing the surface area include a blast treatment using a cut wire, a steel grid, an alumina grid, and the like, an acid treatment using sulfuric acid or hydrochloric acid, a plating treatment using the same element as the substrate, and the like. Although arithmetic mean surface roughness Ra of the surface of a base material is not specifically limited, 0.05 micrometer-50 micrometers are preferable, 0.1-10 micrometers is more preferable, 0.1-8 micrometers is still more preferable.

Next, the case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

In FIG. 43, the first layer 20 serving as the catalyst layer contains at least one oxide of ruthenium oxide, iridium oxide and titanium oxide. Of ruthenium oxide RuO _2, etc., it may be mentioned. IrO ₂ etc. are mentioned as an iridium oxide. Examples of titanium oxides include TiO ₂ . The first layer 20 preferably contains two kinds of oxides of ruthenium oxide and titanium oxide, or three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide. Thereby, the 1st layer 20 becomes a more stable layer, and also adhesiveness with the 2nd layer 30 improves more.

In the case where the first layer 20 includes two kinds of oxides of ruthenium oxide and titanium oxide, titanium contained in the first layer 20 with respect to one mole of ruthenium oxide included in the first layer 20. It is preferable that it is 1-9 mol, and, as for an oxide, it is more preferable that it is 1-4 mol. By setting the composition ratio of the two kinds of oxides in this range, the electrolytic electrode 100 exhibits excellent durability.

When the first layer 20 includes three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide, the first layer 20 is included in the first layer 20 with respect to one mole of ruthenium oxide contained in the first layer 20. It is preferable that it is 0.2-3 mol, and, as for the iridium oxide used, it is more preferable that it is 0.3-2.5 mol. Moreover, it is preferable that it is 0.3-8 mol, and, as for 1 mol of titanium oxide contained in the 1st layer 20 with respect to 1 mol of ruthenium oxide contained in the 1st layer 20, it is more preferable. By making the composition ratio of three types of oxides into this range, the electrode 100 for electrolysis shows the outstanding durability.

When the 1st layer 20 contains at least 2 types of oxide chosen from a ruthenium oxide, an iridium oxide, and a titanium oxide, it is preferable that these oxides form a solid solution. By forming the oxide solid solution, the electrolytic electrode 100 exhibits excellent durability.

In addition to the above composition, as long as it contains at least one oxide of ruthenium oxide, iridium oxide and titanium oxide, those having various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like, referred to as DSA (registered trademark), may be used as the first layer 20.

The first layer 20 does not need to be a single layer, but may include a plurality of layers. For example, the first layer 20 may include a layer containing three kinds of oxides and a layer containing two kinds of oxides. 0.05-10 micrometers is preferable and, as for the thickness of the 1st layer 20, 0.1-8 micrometers is more preferable.

(2nd floor)

It is preferable that the 2nd layer 30 contains ruthenium and titanium. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

It is preferable that the 2nd layer 30 contains palladium oxide, the solid solution of palladium oxide, and platinum, or the alloy of palladium and platinum. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

The longer the longer the thickness of the second layer 30 can maintain the electrolytic performance, the thickness of the second layer 30 is preferably 0.05 to 3 m.

Next, the case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

As a component of the first layer 20 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal include at least one kind, the alloy containing the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide and the platinum group metal is platinum, palladium, rhodium, It is preferable to contain at least 1 type of platinum group metal among ruthenium and iridium.

As a platinum group metal, it is preferable to contain platinum.

It is preferable that a platinum group metal oxide contains ruthenium oxide.

It is preferable that a platinum group metal hydroxide contains a ruthenium hydroxide.

As a platinum group metal alloy, it is preferable to include the alloy of platinum, nickel, iron, and cobalt.

Moreover, it is preferable to contain the oxide or hydroxide of a lanthanoid element as a 2nd component as needed. As a result, the electrolytic electrode 100 exhibits excellent durability.

The oxide or hydroxide of the lanthanoid-based element preferably contains at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium.

Moreover, it is preferable to contain the oxide or hydroxide of a transition metal as a 3rd component as needed.

By adding the third component, the electrolytic electrode 100 exhibits more excellent durability and can reduce the electrolytic voltage.

Examples of preferred combinations include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + platinum + palladium Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium + Sulfur, Ruthenium + Lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + samarium + cobalt, ruthenium + samarium + gallium, ruthenium + samarium + gallium, ruthenium + Samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + Nickel + palladium, bag Gold + nickel + ruthenium, an alloy of platinum and nickel, an alloy of platinum and cobalt, an alloy of platinum and iron, and the like.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal are not included, the main component of the catalyst is preferably nickel element.

It is preferable to contain at least 1 sort (s) among nickel metal, oxide, and hydroxide.

You may add a transition metal as a 2nd component. As a 2nd component to add, it is preferable to contain at least 1 type of element among titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon.

As a preferable combination, nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, etc. are mentioned.

If necessary, an intermediate layer can be formed between the first layer 20 and the electrolytic electrode substrate 10. By providing the intermediate layer, the durability of the electrolytic electrode 100 can be improved.

As an intermediate | middle layer, what has affinity for both the 1st layer 20 and the electrode base material 10 for electrolysis is preferable. As the intermediate layer, nickel oxide, platinum group metal, platinum group metal oxide, and platinum group metal hydroxide are preferable. As an intermediate | middle layer, it can form by apply | coating and baking the solution containing the component which forms an intermediate | middle layer, and can also form a surface oxide layer by heat-processing a base material at 300-600 degreeC in air atmosphere. In addition, it can form by a well-known method, such as a thermal spraying method and an ion plating method.

(2nd floor)

As the components of the first layer 30 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included. Examples of preferred combinations of the elements included in the second layer include combinations exemplified in the first layer. The combination of a 1st layer and a 2nd layer may be a combination with the same composition, and a composition ratio differs, and the combination of a different composition may be sufficient as it.

As thickness of a catalyst layer, the sum total of the formed catalyst layer and the intermediate | middle layer has preferable 0.01 micrometer-20 micrometers. If it is 0.01 micrometer or more, it can fully function as a catalyst. If it is 20 micrometers or less, a strong catalyst layer can be formed with little fall-out from a base material. 0.05 micrometers-15 micrometers are more preferable. More preferably, they are 0.1 micrometer-10 micrometers. More preferably, they are 0.2 micrometer-8 micrometers.

As thickness of an electrode, ie, the thickness of the sum total of an electrolytic electrode base material and a catalyst layer, 315 micrometers or less are preferable, 220 micrometers or less are more preferable, 170 micrometers or less are more preferable from a viewpoint of handling property of an electrode, 150 The thickness is even more preferable, 145 µm or less is particularly preferable, 140 µm or less is still more preferable, 138 µm or less is even more preferable, and 135 µm or less is even more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, it is preferable that it is 130 micrometers or less from a viewpoint similar to the above, More preferably, it is less than 130 micrometers, More preferably, it is 115 micrometers or less, More preferably, it is 65 micrometers or less. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, the thickness of an electrode can be calculated | required by measuring with a dejimatic thickness gauge (Mitsutoyo Corporation, minimum display 0.001 mm). The thickness of the electrode base material for electrodes is measured similarly to electrode thickness. The catalyst layer thickness can be obtained by subtracting the thickness of the electrode base material for electrolysis from the electrode thickness.

In the present embodiment, from the viewpoint of securing sufficient electrolytic performance, the electrode for electrolysis is Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y , Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd It is preferred to include at least one catalyst component selected from the group consisting of Pm, Sm, Eu, Gd, Tb and Dy.

In the present embodiment, the electrode for electrolysis can obtain better handling property as long as it is an electrode having a large elastic deformation region, and has better adhesion force such as a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, a catalyst-free feeder, and the like. From the viewpoint of having a thickness, the thickness of the electrode for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, still more preferably 170 µm or less, even more preferably 150 µm or less, and particularly 145 µm or less. Preferably, 140 micrometers or less are further more preferable, 138 micrometers or less are further more preferable, 135 micrometers or less are further more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, from a viewpoint similar to the above, 130 micrometers or less are preferable, less than 130 micrometers are more preferable, 115 micrometers or less are more preferable, and 65 micrometers or less are still more preferable. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, in this embodiment, a "elastic deformation area | region is wide" means that it is difficult to produce the curvature resulting from winding after winding an electrode for electrolysis to make a winding body, and canceling a wound state. In addition, the thickness of an electrode for electrolysis means the thickness which combined the electrode base material for electrolysis and a catalyst layer, when including the catalyst layer mentioned later.

(Method for producing electrode for electrolysis)

Next, one Embodiment of the manufacturing method of the electrolytic electrode 100 is described in detail.

In the present embodiment, the first layer 20, preferably the second layer (on the electrode base material for electrolysis) is performed by a method such as baking (pyrolysis) of the coating film in an oxygen atmosphere or ion plating, plating, thermal spraying or the like. By forming 30), the electrode 100 for electrolysis can be manufactured. In this manufacturing method of the present embodiment, high productivity of the electrode 100 for electrolysis can be realized. Specifically, a catalyst layer is formed on the electrode base material for electrolysis by a coating step of applying a coating liquid containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing pyrolysis. Pyrolysis means here that the metal salt used as a precursor is heated and decomposed | disassembled into a metal or metal oxide and gaseous substance. Although decomposition products differ depending on the metal species used, the kind of salt, and the atmosphere in which pyrolysis is performed, most metals tend to form oxides in an oxidizing atmosphere. In the industrial production process of electrodes, pyrolysis is usually carried out in air, and in most cases metal oxides or metal hydroxides are formed.

(Formation of the first layer of the anode)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved at least 1 sort (s) of metal salt of ruthenium, iridium, and titanium to an electrolytic electrode base material, and thermally decomposes (baking) in presence of oxygen. The content of ruthenium, iridium and titanium in the first coating liquid is approximately the same as that of the first layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of the second layer)

The 2nd layer 30 is formed as needed, for example, apply | coating the solution containing a palladium compound and a platinum compound, or the solution (2nd coating liquid) containing a ruthenium compound and a titanium compound on the 1st layer 20 After that, it is obtained by pyrolysis in the presence of oxygen.

(Formation of First Layer of Cathode by Pyrolysis)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved the metal salt of various combinations to the electrode base material for electrolysis, and thermally decomposing (baking) in presence of oxygen. The content rate of the metal in a 1st coating liquid is substantially the same as the 1st layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of intermediate layer)

An intermediate | middle layer is formed as needed, for example, is obtained by apply | coating the solution (2nd coating liquid) containing a palladium compound or a platinum compound on a base material, and then thermally decomposing in presence of oxygen. Alternatively, the nickel oxide intermediate layer may be formed on the surface of the substrate only by heating the substrate without applying the solution.

(Formation of First Layer of Cathode by Ion Plating)

The first layer 20 may be formed by ion plating.

As an example, the method of fixing a base material in a chamber, and irradiating an electron beam to a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and ruthenium is deposited on the substrate as ruthenium oxide.

(Formation of First Layer of Cathode by Plating)

The first layer 20 can also be formed by a plating method.

As an example, when a base material is used as a cathode and electrolytic plating is performed in the electrolyte solution containing nickel and tin, alloy plating of nickel and tin can be formed.

(Formation of First Layer of Cathode by Thermal Spray)

The first layer 20 can also be formed by thermal spraying.

As an example, by spraying nickel oxide particles on a substrate, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed.

The electrode for electrolysis in this embodiment can be used integrally with diaphragm, such as an ion exchange membrane and a microporous membrane. Therefore, the laminated body of this embodiment can be used as a membrane integrated electrode, the work which replaces the negative electrode and positive electrode at the time of updating an electrode becomes unnecessary, and work efficiency improves significantly.

Moreover, according to the integral electrode with the diaphragm, such as an ion exchange membrane and a microporous membrane, electrolytic performance can be made to be equivalent to the performance at the time of new, or it can improve.

Hereinafter, the ion exchange membrane will be described in detail.

[Ion exchange membrane]

The ion exchange membrane is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various ion exchange membranes can be applied. In this embodiment, it is preferable to use the membrane main body containing the hydrocarbon type polymer or fluorine-containing polymer which has an ion exchange group, and the ion exchange membrane which has a coating layer formed on at least one surface of this membrane main body. In addition, it is preferable that the coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is 0.1-10 m 2 / g. The ion-exchange membrane of such a structure has little influence on the electrolytic performance by the gas which generate | occur | produces during electrolysis, and it tends to exhibit stable electrolytic performance.

The membrane of the perfluorocarbon polymer into which the ion exchange group is introduced is a sulfonic acid layer having an ion exchange group derived from a sulfo group (group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and an ion exchange group derived from a carboxyl group. It is provided with either a carboxylic sancheung having a - (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). In view of strength and dimensional stability, it is preferable to further have a reinforcing core material.

The inorganic particles and the binder will be described in detail in the description section of the coating layer below.

It is a cross-sectional schematic diagram which shows one Embodiment of an ion exchange membrane. The ion exchange membrane 1 has a membrane main body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group, and coating layers 11a and 11b formed on both surfaces of the membrane main body 10.

In the ion exchange membrane 1, the membrane main body 10 is a sulfonic acid layer 3 having an ion exchange group derived from a sulfo group (a group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and ions derived from a carboxyl group. exchanger has a strength and dimensional stability are enhanced by the carboxylic sancheung 2 provided, and the reinforcement core (4) having a (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). Since the ion exchange membrane 1 is provided with the sulfonic acid layer 3 and the carboxylic acid layer 2, it is suitably used as a cation exchange membrane.

In addition, the ion exchange membrane may have only one of a sulfonic acid layer and a carboxylic acid layer. In addition, the ion exchange membrane does not necessarily need to be reinforced by the reinforcing core, and the arrangement state of the reinforcing core is not limited to the example of FIG. 44.

(The membrane body)

First, the membrane main body 10 constituting the ion exchange membrane 1 will be described.

The membrane main body 10 may have a function of selectively permeating cations, and may include a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group. The structure and the material thereof are not particularly limited, and a suitable one can be appropriately selected. have.

The hydrocarbon-based polymer or fluorine-containing polymer having an ion exchange group in the membrane main body 10 can be obtained from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange precursor which can be an ion-exchange group, for example, by hydrolysis or the like. Specifically, for example, the main chain is made of a fluorinated hydrocarbon, and has a group (ion exchanger precursor) which can be converted into an ion exchanger by hydrolysis or the like as a pendant side chain, and also a polymer which can be melt processed (hereinafter referred to as "fluorine-containing polymer). (a) ") to produce the precursor of the membrane main body 10, and then convert the ion exchanger precursor into the ion exchanger to obtain the membrane main body 10.

The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the third group below. have. Moreover, it can also manufacture by the homopolymerization of 1 type of monomers chosen from any of the following 1st group, the following 2nd group, and the following 3rd group.

As a monomer of a 1st group, a vinyl fluoride compound is mentioned, for example. Examples of the vinyl fluoride compound include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and the like. In particular, when the ion exchange membrane is used as the alkali electrolytic membrane, the vinyl fluoride compound is preferably a perfluoro monomer, and is perfluoro selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Monomer is preferred.

As a monomer of a 2nd group, the vinyl compound which has a functional group which can be converted into a carboxylic acid type ion exchange group (carboxylic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted to a carboxylic acid group, for example, and the like can be _{CF 2 = CF (OCF 2 CYF} ) s -O (CZF) t monomers represented by -COOR (wherein, s is 0 An integer of -2, t represents an integer of 1 to 12, Y and Z each independently represents F or CF ₃ , and R represents a lower alkyl group, for example, a lower alkyl group is an alkyl group having 1 to 3 carbon atoms. .).

Among these, CF is _{2 = CF (OCF 2 CYF)} n -O (CF 2) _m -COOR compound represented by are preferred. Here n represents an integer of 0 to 2, m represents an integer of 1 to 4, Y represents F or CF ₃ , and R represents CH ₃ , C ₂ H ₅ or C ₃ H ₇ .

When the ion exchange membrane is used as a cation exchange membrane for alkali electrolysis, it is preferable to use at least a perfluoro compound as the monomer. However, since the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis, the alkyl group ( R) may not be a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

As a monomer of a 2nd group, the monomer shown below is more preferable among the above.

CF ₂ = CFOCF ₂ -CF (CF ₃ ) OCF ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CF [OCF ₂ -CF (CF ₃ )] ₂ O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₃ COOCH ₃ .

As a monomer of a 3rd group, the vinyl compound which has a functional group which can be converted into a sulfone type ion exchange group (sulfonic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted into a sulfonic acid is, for example, CF ₂ = a monomer represented by the _{CFO-X-CF 2 -SO 2} F are preferred (wherein, X represents an alkylene group of a perfluoroalkyl.). As these specific examples, the monomer etc. which are shown below are mentioned.

CF ₂ = CFOCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CF (CF ₂ ) ₂ SO ₂ F,

CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₂ OCF ₃ ) OCF ₂ CF ₂ SO ₂ F.

Among these, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F are more preferable.

The copolymer obtained from these monomers can be manufactured by the polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, especially the general polymerization method used with respect to tetrafluoroethylene. For example, in the non-aqueous method, inert solvents such as perfluorohydrocarbon and chlorofluorocarbon are used, and in the presence of radical polymerization initiators such as perfluorocarbon peroxide and azo compound, the temperature is 0 to 200 캜 and the pressure is 0.1 to 0.1. The polymerization reaction can be carried out under the condition of 20 MPa.

In the said copolymerization, the kind and ratio of the combination of the said monomers are not specifically limited, It selects according to the kind and quantity of the functional group to provide to the fluorine-containing polymer obtained. For example, in the case of using a fluorine-containing polymer containing only a carboxylic acid group, at least one monomer may be selected and copolymerized from the first group and the second group, respectively. In the case of using a fluorine-containing polymer containing only a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group and the third group, respectively. In the case of using a fluorine-containing polymer having a carboxylic acid group and a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group, the second group, and the third group, respectively. In this case, the target fluorine-containing polymer can also be obtained by separately polymerizing the copolymer composed of the first group and the second group and the copolymer composed of the first group and the third group, and then mixing the copolymer separately. . Moreover, although the mixing ratio of each monomer is not specifically limited, When increasing the quantity of functional groups per unit polymer, what is necessary is just to increase the ratio of the monomer chosen from the said 2nd group and the 3rd group.

Although the total ion exchange capacity of a fluorine-containing copolymer is not specifically limited, It is preferable that it is 0.5-2.0 mg equivalent / g, and it is more preferable that it is 0.6-1.5 mg equivalent / g. Here, total ion exchange capacity means the equivalent of the exchanger per unit weight of dry resin, and can be measured by neutralization titration etc.

In the membrane main body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorine-containing polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorine-containing polymer having a carboxylic acid group are laminated. . By using this layer structure as the membrane main body 10, the selective permeability of cations such as sodium ions can be further improved.

In the case where the ion exchange membrane 1 is disposed in the electrolytic cell, the sulfonic acid layer 3 is usually disposed on the anode side of the electrolytic cell and the carboxylic acid layer 2 on the cathode side of the electrolytic cell.

It is preferable that the sulfonic acid layer 3 is comprised from the material with low electrical resistance, and it is preferable that a film thickness is thicker than the carboxylic acid layer 2 from a viewpoint of film strength. The film thickness of the sulfonic acid layer 3 becomes like this. Preferably it is 2-25 times of the carboxylic acid layer 2, More preferably, it is 3-15 times.

It is preferable that the carboxylic acid layer 2 has high anion exclusion property even if it is thin. Anion-exclusion here means the property which wants to interrupt the invasion and permeation | transmission of anion to the ion exchange membrane 1. In order to improve anion exclusion, disposing a carboxylic acid layer having a small ion exchange capacity with respect to the sulfonic acid layer is effective.

As the fluorine-containing polymer used for the sulfonic acid layer 3, for example, a polymer obtained by using CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F as the third group of monomers is suitable.

Carboxylic acids referred to as the fluorine-based polymer for use in sancheung (2) is, for example, as monomers of group 2 _{CF 2 = CFOCF 2 CF (CF} 2) O (CF 2) a polymer obtained by using ₂ COOCH ₃ are suitable.

(Coating layer)

It is preferable that an ion exchange membrane has a coating layer on at least one surface of a membrane main body. 44, in the ion exchange membrane 1, the coating layers 11a and 11b are formed on both surfaces of the membrane main body 10, respectively.

The coating layer includes inorganic particles and a binder.

As for the average particle diameter of an inorganic particle, it is more preferable that it is 0.90 micrometer or more. If the average particle diameter of the inorganic particles is 0.90 µm or more, the durability against impurities as well as gas adhesion is greatly improved. In other words, a particularly significant effect is obtained by increasing the average particle diameter of the inorganic particles and by satisfying the above-described specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by crushing gemstones can be used. Preferably, the inorganic particles obtained by gemstone grinding can be suitably used.

In addition, the average particle diameter of an inorganic particle can be 2 micrometers or less. If the average particle diameter of an inorganic particle is 2 micrometers or less, it can prevent that a film | membrane is damaged by an inorganic particle. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 µm.

Here, an average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation).

It is preferable that the shape of an inorganic particle is an irregular shape. Resistance to impurities is further improved. In addition, the particle size distribution of the inorganic particles is preferably wide.

It is preferable that an inorganic particle contains at least 1 sort (s) of inorganic substance chosen from the group which consists of an oxide of a group IV element of a periodic table, a nitride of a group IV element of a periodic table, and a carbide of a group IV element of a periodic table. More preferably, they are particles of zirconium oxide from the viewpoint of durability.

It is preferable that this inorganic particle is an inorganic particle manufactured by crushing the gemstone of an inorganic particle, or it is preferable to make spherical particle | grains of the uniform diameter of particle | grains into an inorganic particle by melting and refine | purifying the gemstone of an inorganic particle.

Examples of the raw material grinding method include, but are not particularly limited to, ball mills, bead mills, colloid mills, conical mills, disc mills, edge mills, milling mills, hammer mills, pellet mills, VSI mills, willy mills, roller mills, and jet mills. Etc. can be mentioned. Moreover, it is preferable to wash | clean after grinding | pulverization, and it is preferable to be acid-processed at that time. As a result, impurities such as iron adhering to the surface of the inorganic particles can be reduced.

The coating layer preferably comprises a binder. A binder is a component which keeps inorganic particle on the surface of an ion exchange membrane, and comprises a coating layer. It is preferable that a binder contains a fluorine-containing polymer from a viewpoint of resistance to electrolyte solution or the product by electrolysis.

As a binder, it is more preferable that it is a fluorine-containing polymer which has a carboxylic acid group or a sulfonic acid group from a tolerance with respect to the electrolyte solution and the product by electrolysis, and adhesiveness to the surface of an ion exchange membrane. When forming a coating layer on the layer (sulfonic acid layer) containing a fluorine-containing polymer which has a sulfonic acid group, it is more preferable to use the fluorine-containing polymer which has a sulfonic acid group as a binder of this coating layer. Moreover, when forming a coating layer on the layer (carboxylic acid layer) containing the fluorine-containing polymer which has a carboxylic acid group, it is more preferable to use the fluorine-containing polymer which has a carboxylic acid group as a binder of this coating layer.

It is preferable that it is 40-90 mass%, and, as for content of an inorganic particle in a coating layer, it is more preferable that it is 50-90 mass%. Moreover, it is preferable that it is 10-60 mass%, and, as for content of a binder, it is more preferable that it is 10-50 mass%.

The distribution density of the coating layer in the ion exchange membrane is preferably 0.05 to 2 mg per cm 2. In addition, when an ion exchange membrane has a concave-convex shape on the surface, it is preferable that the distribution density of a coating layer is 0.5-2 mg per cm <2>.

It does not specifically limit as a method of forming a coating layer, A well-known method can be used. For example, the method of apply | coating the coating liquid which disperse | distributed inorganic particle to the solution containing a binder by spray etc. is mentioned.

(Reinforced heartwood)

It is preferable that the ion exchange membrane has a reinforcing core material disposed inside the membrane body.

The reinforcing core is a member for enhancing the strength and dimensional stability of the ion exchange membrane. By arrange | positioning a reinforcing core material inside a membrane main body, especially expansion and contraction of an ion exchange membrane can be controlled to a desired range. Such an ion exchange membrane can maintain excellent dimensional stability for a long time without being stretched more than necessary in electrolysis or the like.

The configuration of the reinforcing core is not particularly limited, and may be formed by spinning a yarn called reinforcing yarn, for example. The reinforcement yarn mentioned here is a member which constitutes a reinforcing core material, which can impart desired dimensional stability and mechanical strength to the ion exchange membrane, and refers to a yarn that can stably exist in the ion exchange membrane. By using the reinforcing core material which radiated such reinforcement yarn, further excellent dimensional stability and mechanical strength can be provided to the ion exchange membrane.

The material of the reinforcing core material and the reinforcing yarn used for this is not particularly limited, but it is preferable that the material is resistant to acids, alkalis, or the like. desirable.

Examples of the fluorine-containing polymer used in the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether polymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetra Fluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, vinylidene fluoride polymer (PVDF), and the like. Among these, it is preferable to use the fiber which consists of polytetrafluoroethylene from a heat resistant and chemical resistant viewpoint especially.

The diameter of the reinforcing sand used for the reinforcing core is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The weave density (number of insertion lines per unit length) is preferably 5 to 50 lines / inch. The form of the reinforcing core is not particularly limited, and for example, a woven fabric, a nonwoven fabric, a knitted fabric, or the like is used, but it is preferably a form of a woven fabric. In addition, the thickness of the woven fabric is preferably 30 to 250 m, more preferably 30 to 150 m.

As the woven fabric or knitted fabric, monofilament, multifilament or yarns, slit yarns, and the like thereof can be used, and the weaving method can use various weaving methods such as plain weave, leno weave, knitting, cord weave, and seerker.

The weaving method and arrangement of the reinforcing core material in the membrane main body are not particularly limited and can be appropriately arranged in consideration of the size and shape of the ion exchange membrane, the desired physical properties and the use environment for the ion exchange membrane, and the like.

For example, the reinforcing core may be disposed along a predetermined direction of the membrane body, but from the viewpoint of dimensional stability, the reinforcing core is disposed along the predetermined first direction, and a second direction substantially perpendicular to the first direction is provided. Therefore, it is preferable to arrange a separate reinforcing core material. By arranging the plurality of reinforcing cores so as to run substantially straight inside the longitudinal membrane body of the membrane body, further superior dimensional stability and mechanical strength can be imparted in multiple directions. For example, an arrangement for weaving the reinforcing core material (warp) disposed along the longitudinal direction and the reinforcing core material (weft) arranged along the transverse direction on the surface of the membrane body is preferable. Lion weaved by inserting the same number of wefts into the weaving plain weave by twisting and inserting warp and weft alternately, or by weaving two warp and leno weaving by twisting two warp and two or several lines. It is more preferable to use a woven fabric (a loom) from the viewpoint of dimensional stability, mechanical strength, and ease of manufacture.

In particular, it is preferable that the reinforcing core is disposed along both directions of the MD direction (Machine Direction direction) and the TD direction (Transverse Direction direction) of the ion exchange membrane. That is, it is preferable to be woven in the MD direction and the TD direction. Here, MD direction means the direction (flow direction) in which a membrane main body and various core materials (for example, a reinforced core material, a reinforcement yarn, a sacrificial yarn etc. mentioned later) are conveyed in the manufacturing process of the ion exchange membrane mentioned later, and a TD direction is It refers to a direction approximately perpendicular to the MD direction. The yarn woven along the MD direction is called MD yarn, and the yarn woven along the TD direction is called TD yarn. Usually, the ion exchange membrane used for electrolysis is rectangular, and a longitudinal direction becomes MD direction, and the width direction becomes a TD direction in many cases. By weaving the reinforced MD core material and the reinforced TD core material, it is possible to give even more excellent dimensional stability and mechanical strength in multiple directions.

The spacing of the reinforcing cores is not particularly limited and can be appropriately arranged in consideration of desired physical properties, use environment, and the like for the ion exchange membrane.

The opening ratio of the reinforcing core material is not particularly limited, and is preferably 30% or more, more preferably 50% or more and 90% or less. The opening ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane.

The opening ratio of the reinforcing core is the total area (B) of the surface through which substances such as ions (electrolyte and cation (for example, sodium ions) contained) in the area (A) of either surface of the membrane body can pass. The ratio of (B / A). The total area (B) of the surface through which substances such as ions can pass can be referred to as the total area of the region where cations, electrolytes, and the like are not blocked by the reinforcing core included in the ion exchange membrane.

45 is a schematic view for explaining the aperture ratio of the reinforcing core material constituting the ion exchange membrane. 45 enlarges a part of the ion exchange membrane and shows only the arrangement of the reinforcing core materials 21 and 22 in the region, and the illustration of other members is omitted.

The total area C of the reinforcement core from the area A of the region including the area of the reinforcement core, which is also surrounded by the reinforcement core 21 arranged in the longitudinal direction and the reinforcement core 22 arranged in the horizontal direction. By subtracting, the total area B of the area through which substances such as ions in the area A of the area can pass can be obtained. That is, an opening ratio can be calculated | required by following formula (I).

Aperture ratio = (B) / (A) = ((A)-(C)) / (A). (I)

Among the reinforcing cores, a particularly preferable form is a tape yarn or a highly oriented monofilament containing PTFE in view of chemical resistance and heat resistance. Specifically, a high-strength porous sheet made of PTFE is a tape yarn slitted in tape form, or a 50 to 300 denier of a highly oriented monofilament made of PTFE, and a woven density of 10 to 50 lines / inch. It is more preferable that it is a reinforcement core material whose thickness is the range of 50-100 micrometers. It is more preferable that the opening ratio of the ion exchange membrane including such a reinforcing core material is 60% or more.

Examples of the shape of the reinforcing yarn include round yarns and tape-like yarns.

(Communication hole)

It is preferable that the ion exchange membrane has a communication hole inside the membrane main body.

The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, a communication hole is a tubular hole formed in the inside of a membrane main body, and is formed by eluting the sacrificial core material (or sacrificial thread) mentioned later. The shape and diameter of the communication hole can be controlled by selecting the shape and diameter of the sacrificial core material (sacrificial yarn).

By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured at the time of electrolysis. Although the shape of a communication hole is not specifically limited, According to the manufacturing method mentioned later, it can be set as the shape of the sacrificial core material used for formation of a communication hole.

The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With such a structure, in the part where the communication hole is formed in the cathode side of the reinforcing core material, ions (for example, sodium ions) transported through the electrolyte solution filled in the communication hole can also flow to the cathode side of the reinforcing core material. As a result, since the flow of cation is not blocked, the electrical resistance of the ion exchange membrane can be made lower.

The communication hole may be formed along only one predetermined direction of the membrane main body constituting the ion exchange membrane, but is formed in both the longitudinal direction and the transverse direction of the membrane main body in view of exhibiting more stable electrolytic performance. desirable.

[Production method]

As a suitable manufacturing method of an ion exchange membrane, the method of having the following (1) process-(6) process is mentioned.

(1) Process: The process of manufacturing the fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(2) Process: If necessary, a sacrificial yarn is disposed between adjacent reinforcing cores by at least weaving a plurality of reinforcing cores and a property of dissolving in an acid or alkali and forming at least a communication hole. To obtain the finished reinforcement.

(3) Process: The process of film-forming the said fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(4) Step: The step of embedding the reinforcing material in the film as necessary to obtain a membrane body having the reinforcing material disposed therein.

(5) Process: The process (hydrolysis process) of hydrolyzing the membrane main body obtained at process (4).

(6) Process: The process (coating process) of forming a coating layer in the film main body obtained at the process (5).

Hereinafter, each process is explained in full detail.

(1) Process: process for producing fluorine-containing polymer

In the step (1), the fluorine-containing polymer is produced by using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of a fluorine-containing polymer, in the manufacture of the fluorine-containing polymer which forms each layer, the mixing ratio of the monomer of a raw material may be adjusted.

(2) Process: manufacturing process of reinforcement

A reinforcing material is a woven fabric etc. which woven the reinforcement yarn. The reinforcing material is embedded in the film to form the reinforcing core material. When using an ion exchange membrane having communication holes, the sacrificial yarn is also woven into the reinforcing material. In this case, the blending amount of the sacrificial material is preferably 10 to 80 mass%, more preferably 30 to 70 mass% of the entire reinforcing material. By weaving a sacrificial thread, the mesh shift | offset of a reinforcement core material can also be prevented.

The sacrificial material has solubility in a film production process or an electrolytic environment, and rayon, polyethylene terephthalate (PET), cellulose, polyamide, and the like are used. Moreover, polyvinyl alcohol etc. which have a thickness of 20-50 denier and consist of monofilament or multifilament are also preferable.

In the step (2), by adjusting the arrangement of the reinforcing core material or the sacrificial material, the opening ratio, the arrangement of the communication holes, and the like can be controlled.

(3) process: filming process

In the step (3), the fluorine-containing polymer obtained in the step (1) is filmed using an extruder. A single layer structure may be sufficient as a film, and as above-mentioned, the two-layered structure of a sulfonic acid layer and a carboxylic acid layer may be sufficient, and the multilayered structure of three or more layers may be sufficient as it.

As a method of film-forming, the following are mentioned, for example.

A method of filming each of the fluorine-containing polymer having a carboxylic acid group and the fluorine-containing polymer having a sulfonic acid group separately.

A method in which a fluorine-containing polymer having a carboxylic acid group and a fluorine-containing polymer having a sulfonic acid group are co-extruded into a composite film.

In addition, a plurality of films may be sufficient respectively. Moreover, coextrusion of different kinds of films is preferable because it contributes to raising the adhesive strength of an interface.

(4) step: the step of obtaining the membrane body

In the step (4), the film body in which the reinforcing material is embedded is obtained by embedding the reinforcing material obtained in the step (2) inside the film obtained in the step (3).

As a preferable formation method of a film main body, (i) the fluorine-containing polymer which has a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) located in the cathode side (henceforth, the layer which consists of this is called a 1st layer), And forming a fluorine-containing polymer having a sulfonic acid group precursor (e.g., a sulfonylfluoride functional group) (hereinafter, referred to as a second layer) by a coextrusion method, and heating and vacuum source as necessary. Is laminated on a flat plate or drum having a large number of pores on the surface of the reinforcing material and the second layer / first layer composite film in the order of a reinforcing material and a heat-resistant release paper having air permeability. Integrating while removing air between each layer by decompression under temperature; (ii) Apart from the second layer / first layer composite film, the fluorine-containing polymer (third layer) having a sulfonic acid group precursor is previously filmed alone, and the surface is heated and heated using a vacuum source if necessary. The laminated film was laminated in the order of a composite film consisting of a third layer film, a reinforcing core material, and a second layer / first layer via a heat-resistant release paper having air permeability on a flat plate or a drum having a large number of pores thereon. The method of integrating, removing the air between each layer by pressure reduction under the temperature which melt | dissolves is mentioned.

Here, coextrusion of a 1st layer and a 2nd layer contributes to raising the adhesive strength of an interface.

Moreover, the method of integrating under reduced pressure has the feature that the thickness of the 3rd layer on a reinforcement material becomes large compared with the pressure press method. In addition, since the reinforcing material is fixed to the inner surface of the membrane main body, it has the performance of sufficiently maintaining the mechanical strength of the ion exchange membrane.

In addition, the variation of lamination described here is an example, and considering the desired layer structure, physical properties, etc. of a film body, a suitable lamination pattern (for example, the combination of each layer, etc.) can be selected, and then co-extruded.

Further, in order to further improve the electrical performance of the ion exchange membrane, a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is further interposed between the first layer and the second layer. It is also possible to use a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor instead of the layer.

The method for forming the fourth layer may be a method of separately preparing a fluorine-containing polymer having a carboxylic acid group precursor and a fluorine-containing polymer having a sulfonic acid group precursor, and then mixing the monomers with the carboxylic acid group precursor and the sulfonic acid group precursor. The method of copolymerizing the monomer which has the thing may be used.

In the case where the fourth layer is configured as an ion exchange membrane, the coextruded film of the first layer and the fourth layer is molded, and the third layer and the second layer are filmed independently of this, by the method described above. You may laminate | stack and three layers of a 1st layer / 4th layer / 2nd layer may be film-formed by coextrusion at once.

In this case, the direction in which the extruded film flows is the MD direction. In this way, a membrane body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material.

In addition, the ion exchange membrane preferably has a protruding portion, that is, a convex portion, made of a fluorine-containing polymer having a sulfonic acid group, on the surface side of the sulfonic acid layer. It does not specifically limit as a method of forming such a convex part, The well-known method of forming a convex part in the resin surface can be employ | adopted. Specifically, the method of embossing on the surface of a film main body is mentioned, for example. For example, when the said composite film, reinforcing material, etc. are integrated, the said convex part can be formed by using the release paper previously embossed. When forming a convex part by embossing, control of the height and placement density of a convex part can be performed by controlling the emboss shape (shape of a release paper) to be transferred.

(5) hydrolysis process

In the step (5), the membrane body obtained in the step (4) is hydrolyzed to convert the ion exchanger precursor into the ion exchanger (hydrolysis step).

In the step (5), the elution hole can be formed in the membrane main body by dissolving and removing the sacrificial yarn contained in the membrane main body with an acid or an alkali. In addition, the sacrificial yarn may remain in the communication hole without being completely dissolved and removed. In addition, the sacrificial yarn remaining in the communication hole may be dissolved and removed by the electrolytic solution when the ion exchange membrane is provided for electrolysis.

The sacrificial yarn is soluble in acid or alkali in the ion exchange membrane production process or in an electrolytic environment, and communication holes are formed in the site by dissolving the sacrificial material.

The step (5) can be performed by immersing the membrane body obtained in the step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (dimethyl sulfoxide) can be used.

It is preferable that the said mixed solution contains 2.5-4.0 N of KOH, and contains 25-35 mass% of DMSO.

As temperature of hydrolysis, it is preferable that it is 70-100 degreeC. The higher the temperature, the thicker the apparent thickness. More preferably, it is 75-100 degreeC.

It is preferable that it is 10 to 120 minutes as time of hydrolysis. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes.

Here, the process of forming a communication hole by eluting a sacrificial yarn is demonstrated in detail. 46A and 46B are schematic views for explaining a method of forming communication holes of an ion exchange membrane.

46A and 46B, only the communication hole 504 formed by the reinforcement yarn 52, the sacrificial yarn 504a, and the sacrificial yarn 504a is shown, and it is shown to other members, such as a membrane main body. The illustration is omitted.

First, the reinforcement yarn 52 which comprises a reinforcing core material in an ion exchange membrane, and the sacrificial yarn 504a for forming the communication hole 504 in an ion exchange membrane are used as a knitted reinforcement material. And the communication hole 504 is formed by eluting the sacrificial yarn 504a in the process (5).

According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a may be adjusted in accordance with the arrangement of the reinforcing core and the communication hole in the membrane main body of the ion exchange membrane.

In FIG. 46 (a), although the reinforcement of the plain weave which woven the reinforcement yarn 52 and the sacrificial yarn 504a in both the longitudinal direction and the horizontal direction in the ground is illustrated, the reinforcement yarn in a reinforcement material as needed. The arrangement of the 52 and the victim 504a can be changed.

(6) coating process

In the step (6), the coating layer can be formed by preparing a coating liquid containing the inorganic particles obtained by gemstone grinding or melting of the gemstone and a binder, and applying and drying the coating liquid on the surface of the ion exchange membrane obtained in the step (5). .

As a binder, after hydrolyzing the fluorine-containing polymer having an ion exchange group precursor with an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH), it is immersed in hydrochloric acid to replace the counter ion of the ion exchange group with H ⁺ . One binder (eg, a fluorine-containing polymer having a carboxyl or sulfo group) is preferred. Since it becomes easy to melt | dissolve in water and ethanol mentioned later by this, it is preferable.

This binder is dissolved in a solution in which water and ethanol are mixed. Moreover, the preferable volume ratio of water and ethanol is 10: 1-1:10, More preferably, it is 5: 1-1: 5, More preferably, it is 2: 1-1: 2. In the solution thus obtained, the inorganic particles are dispersed by a ball mill to obtain a coating solution. At this time, the average particle diameter of a particle | grains, etc. can also be adjusted by adjusting the time and the rotation speed at the time of dispersion. In addition, the preferable compounding quantity of an inorganic particle and a binder is as above-mentioned.

The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, but is preferably a light coating liquid. Thereby, it becomes possible to apply | coat uniformly to the surface of an ion exchange membrane.

In addition, when dispersing the inorganic particles, a surfactant may be added to the dispersion. As surfactant, a nonionic surfactant is preferable, For example, HS-210, NS-210, P-210, E-212 by Nichi-yu Corporation, etc. are mentioned.

An ion exchange membrane is obtained by apply | coating the obtained coating liquid to the surface of an ion exchange membrane by spray coating or roll coating.

[Microporous membrane]

As described above, the microporous membrane of the present embodiment is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various microporous membranes can be applied.

Although the porosity of the microporous membrane of this embodiment is not specifically limited, For example, it can be 20-90, Preferably it is 30-85. The porosity can be calculated by the following formula, for example.

Porosity = (1- (Dry Film Weight in Dry State) / (Volume calculated from the thickness, width and length of the film and weight calculated from the density of the film material)) × 100

Although the average pore diameter of the microporous membrane of this embodiment is not specifically limited, For example, it can be 0.01 micrometer-10 micrometers, Preferably it is 0.05 micrometer-5 micrometers. The average pore diameter is, for example, the film is vertically cut in the thickness direction, and the cut surface is observed by FE-SEM. It can obtain | require by measuring and averaging about 100 points of the diameter of the hole observed.

Although the thickness of the microporous film of this embodiment is not specifically limited, For example, it can be 10 micrometers-1000 micrometers, Preferably it is 50 micrometers-600 micrometers. The said thickness can be measured using a micrometer (made by Mitsutoyo Corporation) etc., for example.

Specific examples of the microporous membranes described above include Agir's Zirfon Perl UTP 500 (also referred to as Zirfon membrane in this embodiment), International Publication No. 2013-183584, International Publication No. 2016-203701, etc. The things described are mentioned.

In this embodiment, it is preferable that a diaphragm contains the 1st ion exchange resin layer and the 2nd ion exchange resin layer which has EW (ion exchange equivalent) different from this 1st ion exchange resin layer. Moreover, it is preferable that a diaphragm contains the 1st ion exchange resin layer and the 2nd ion exchange resin layer which has a functional group different from this 1st ion exchange resin layer. An ion exchange equivalent can be adjusted with the functional group to introduce | transduce, and the functional group which can be introduce | transduced is as above-mentioned.

[Fixed area]

In this embodiment, the electrode for electrolysis is fixed to at least one area | region of the surface of a diaphragm, and in the term of <third embodiment>, this one or two or more area | regions is also called fixed area | region. The fixed region in the present embodiment has a function of suppressing separation of the electrode for electrolysis and the diaphragm, and is not particularly limited as long as it is a portion for fixing the electrode for electrolysis to the diaphragm. In some cases, the fixing member, which is separate from the electrolytic electrode, is used as the fixing means. In addition, the fixed area | region in this embodiment may exist only in the position corresponding to the energized surface at the time of electrolysis, and may extend to the position corresponding to the non-electrically conductive surface. In addition, the "conduction surface" corresponds to the part designed to allow the movement of the electrolyte between the anode chamber and the cathode chamber. In addition, a "non-electrically conductive surface" means parts other than an electrically conductive surface.

In addition, in this embodiment, the ratio of the fixed area | region on the surface of a diaphragm (henceforth simply "ratio (alpha)") becomes more than 0% and less than 93%. The said ratio can be calculated | required as ratio of the area of the fixed area | region (henceforth simply "area S3") with respect to the area of the diaphragm surface (henceforth simply "area S1"). In this embodiment, the "surface of a diaphragm" means the surface in which the electrode for electrolysis exists among the surfaces which a diaphragm has. In addition, on the surface of the above-mentioned diaphragm, the area of the part which is not covered by the electrode for electrolysis is also counted as area S1.

From a viewpoint of making it more stable as a laminated body of a diaphragm and an electrode for electrolysis, the said ratio (= 100 * S3 / S1) is more than 0%, Preferably it is 0.00000001% or more, More preferably, it is 0.0000001% or more. On the other hand, as in the prior art, when the front surface of the contact surface of the diaphragm and the electrode is firmly adhered by a method such as thermocompression bonding (that is, the ratio becomes 100%), the front surface of the contact surface on the electrode The membrane is embedded in the diaphragm to be physically bonded. This adhesive portion interferes with the movement of sodium ions in the film, and the voltage is greatly increased. In the present embodiment, from the viewpoint of ensuring a sufficient space for the ions to move freely, the ratio is less than 93%, preferably 90% or less, more preferably 70% or less, even more preferably less than 60% to be.

In the present embodiment, from the viewpoint of obtaining better electrolytic performance, it is preferable to adjust the area (hereinafter, also simply referred to as "area S3 '") of the area of the fixed area (area S3) corresponding only to the conductive surface. Do. That is, it is preferable to adjust the ratio of the area S3 'to the area of the energizing surface (hereinafter also simply referred to as "area S2") (hereinafter also simply referred to as "ratio β"). In addition, area S2 can be specified as the surface area of an electrode for electrolysis (details are mentioned later). Specifically, in the present embodiment, the ratio β (= 100 x S3 '/ S2) is preferably more than 0% and less than 100%, more preferably 0.0000001% or more and less than 83%, still more preferably 0.000001% or more 70 It is% or less, More preferably, it is 0.00001% or more and 25% or less.

Said ratio (alpha) and (beta) can be measured as follows, for example.

First, the area S1 of the surface of the diaphragm is calculated. Next, the area S2 of the electrode for electrolysis is calculated. Here, the areas S1 and S2 can be identified as areas when the laminate of the diaphragm and the electrode for electrolysis is viewed from the electrode side for electrolysis (see FIG. 57).

In addition, the shape of the electrode for electrolysis is not particularly limited, but may be one having pores, and the case is one having pores such as a reticular shape. (I) When the porosity is less than 90%, S2 (2) When the porosity is 90% or more, S2 is calculated by the area excluding the perforated part in order to sufficiently secure the electrolytic performance. The porosity here is a numerical value (%; 100 x S ') obtained by dividing the total area S' of the openings in the electrode for electrolysis by the area S '' in the electrode for electrolysis obtained by counting the openings with an area. / S '').

The area (area S3 and area S3 ') of the fixed region will be described later.

As mentioned above, ratio (%) of the said area | region in the surface of a diaphragm can be calculated | required by calculating 100 * (S3 / S1). Moreover, as ratio (%) of the area of the part corresponding only to the electrically conductive surface of the fixed area with respect to the area of an electrically conductive surface, it can obtain | require by calculating 100x (S3 '/ S2).

More specifically, it can measure by the method as described in the Example mentioned later.

Although the area S1 of the surface of the diaphragm identified as mentioned above is not specifically limited, It is preferable that they are 1 times or more and 5 times or less of the area S2 of an electricity supply surface, More preferably, they are 1 times or more and 4 times or less, More preferably, Is more than 1 time and less than 3 times.

In this embodiment, although the fixing structure in a fixed area | region is not limited, For example, the fixing structure illustrated below can be employ | adopted. In addition, only 1 type may be employ | adopted for each fixing structure, and may be employ | adopted in combination of 2 or more type.

In this embodiment, it is preferable that at least one part of the electrode for electrolysis is fixed through the diaphragm in the fixed area | region. This aspect is demonstrated using FIG. 47A.

In FIG. 47A, at least a part of the electrolytic electrode 2 is fixed through the diaphragm 3. As shown in FIG. 47A, a part of the electrolytic electrode 2 penetrates through the diaphragm 3. 47A shows an example in which the electrolytic electrode 2 is a metal porous electrode. That is, although the part of the electrode for electrolysis 2 is shown independently in FIG. 47A, these are connected and have shown the cross section of the integral metal porous electrode (it is the same also in FIGS. 48-51 below).

In such an electrode structure, for example, when the diaphragm 3 at a predetermined position (position to be a fixed region) is pressed against the electrolytic electrode 2, the diaphragm is formed in the uneven structure or the hole structure of the surface of the electrolytic electrode 2. A part of (3) enters, and the recessed part of the electrode surface and the convex part around a hole penetrate the diaphragm 3, Preferably it penetrates out to the outer surface 3b of the diaphragm 3, as shown in FIG. 47A. .

As described above, the fixed structure of FIG. 47A can be manufactured by pressing the diaphragm 3 against the electrolytic electrode 2, but in this case, the thermocompression bonding and heat suction in the state which softened the diaphragm 3 by heating. do. As a result, the electrolytic electrode 2 penetrates through the diaphragm 3. Alternatively, the membrane 3 may be melted. In this case, it is preferable to suck the diaphragm 3 from the outer surface 2b side (back side) of the electrode 2 for electrolysis in the state shown in FIG. 47B. Moreover, the area | region which pressed the diaphragm 3 to the electrolytic electrode 2 comprises a "fixed area | region."

The fixed structure shown in FIG. 47A can be observed with a magnifying glass (loupe), an optical microscope, or an electron microscope. In addition, when the electrolytic electrode 2 penetrates through the diaphragm 3, for the conduction test using a tester or the like between the outer surface 3b of the diaphragm 3 and the outer surface 2b of the electrolytic electrode 2. By this, it is possible to infer the fixing structure of Fig. 47A.

In Fig. 47A, it is preferable that the electrolyte solution of the anode chamber and the cathode chamber partitioned by the diaphragm does not penetrate the through portion. For this reason, it is preferable that the hole diameter of the part which penetrated is small so that electrolyte solution does not permeate | transmit. Specifically, when performing an electrolytic test, it is preferable that the performance equivalent to the diaphragm which does not have a penetration part is exhibited. Or it is preferable to process to prevent permeation | transmission of electrolyte solution to the part which penetrated. It is preferable to use the material which does not elute and decompose | dissolve by the anode chamber electrolyte solution, the product which arises in a cathode chamber, the cathode chamber electrolyte solution, and the product which generate | occur | produces in the penetrating part. For example, EPDM and fluorine resin are preferable. It is more preferable that it is a fluororesin which has an ion exchange group.

In this embodiment, it is preferable that at least one part of the electrode for electrolysis is located inside and fixed to a diaphragm in a fixed area | region. This aspect is demonstrated using FIG. 48A.

As described above, the surface of the electrolytic electrode 2 has an uneven structure or a hole structure. In the embodiment shown in FIG. 48A, a part of the electrode surface penetrates into and is fixed to the diaphragm 3 at a predetermined position (a position that should be a fixed region). The fixed structure shown in FIG. 48A can be manufactured by pressing the diaphragm 3 on the electrode 2 for electrolysis. In this case, it is preferable to form the fixed structure of FIG. 48A by thermocompression bonding and heat suction in the state which softened the diaphragm 3 by heating. Alternatively, the diaphragm 3 may be melted to form the fixed structure of FIG. 48A. In this case, it is preferable to suck the diaphragm 3 from the outer surface 2b side (back side) of the electrode 2 for electrolysis.

The fixed structure shown in FIG. 48A can be observed with a magnifying glass (loupe), an optical microscope, or an electron microscope. In particular, after embedding the sample, a method of creating and observing a cross section by a microtome is preferable. In addition, in the fixed structure shown in FIG. 48A, since the electrolytic electrode 2 does not penetrate the diaphragm 3, the outer surface 3b of the diaphragm 3 and the outer surface 2b of the electrolytic electrode 2 are shown. The conduction by the conduction test between is not confirmed.

In this embodiment, it is preferable to further have a fixing member for fixing a diaphragm and an electrode for electrolysis. This aspect is demonstrated using FIGS. 49A-C.

The fixing structure shown in FIG. 49A uses the fixing member 7 which is separate from the electrolytic electrode 2 and the diaphragm 3, and the fixing member 7 is the electrolytic electrode 2 and the diaphragm 3 ) It is a structure fixed through. The electrolytic electrode 2 does not necessarily need to penetrate through the fixing member 7, but may be fixed so as not to be separated from the diaphragm 3 by the fixing member 7. The material of the fastening member 7 is not specifically limited, As the fastening member 7, what consists of metal, resin, etc. can be used, for example. In the case of a metal, nickel, nichrome, titanium, stainless steel (SUS), etc. are mentioned. These oxides may be sufficient. Examples of the resin include fluororesins (e.g. PTFE (polytetrafluoroethylene), PFA (copolymer of tetrafluoroethylene and perfluoroalkoxy ethylene), ETFE (copolymer of tetrafluoroethylene and ethylene), The material of the diaphragm 3 described below, PVDF (polyvinylidene fluoride), EPDM (ethylene propylene diene rubber), PP (polyethylene), PE (polypropylene), nylon, aramid, etc. can be used.

In the present embodiment, for example, using a thread-shaped fixing member (thread-shaped metal or resin), as shown in Figs. 49B and C, the outer surfaces 2b of the electrolytic electrode 2 and the diaphragm 3, It can also fix by sewing the predetermined position (position which should become a fixed area | region) between 3b). Although it does not specifically limit as thread-shaped resin, For example, the thread of PTFE etc. are mentioned. It is also possible to fix the electrolytic electrode 2 and the diaphragm 3 using a fixing mechanism such as a tacker.

49A to 49C, it is preferable that the electrolyte solution of the anode chamber and the cathode chamber partitioned by the diaphragm does not penetrate the penetrating portion. For this reason, it is preferable that the hole diameter of the part which penetrated is small so that electrolyte solution does not permeate | transmit. Specifically, when performing an electrolytic test, it is preferable that the performance equivalent to the diaphragm which does not have a penetration part is exhibited. Or it is preferable to process to prevent permeation | transmission of electrolyte solution to the part which penetrated. It is preferable to use the material which does not elute and decompose | dissolve by the anode chamber electrolyte solution, the product which arises in a cathode chamber, the cathode chamber electrolyte solution, and the product which generate | occur | produces in the penetrating part. For example, EPDM and fluorine resin are preferable. It is more preferable that it is a fluororesin which has an ion exchange group.

The fixed structure shown in FIG. 50 is a structure in which an organic resin (adhesive layer) is interposed and fixed between the electrode 2 for electrolysis and the diaphragm 3. That is, in FIG. 50, the organic resin as the fixing member 7 is arranged at a predetermined position (position to be a fixed region) between the electrolytic electrode 2 and the diaphragm 3 and fixed by adhesion. . For example, both or one of the inner surface 2a of the electrolytic electrode 2 or the inner surface 3a of the diaphragm 3 or the inner surfaces 2a and 3a of the electrolytic electrode 2 and the diaphragm 3. The organic resin is applied to the. And the fixed structure shown in FIG. 50 can be formed by joining the electrolytic electrode 2 and the diaphragm 3. Although the material of an organic resin is not specifically limited, For example, fluororesin (for example, PTFE, PFA, ETFE), resin similar to the material which comprises the above-mentioned diaphragm 3, etc. can be used. In addition, a commercially available fluorine adhesive, a PTFE dispersion, or the like can also be used as appropriate. In addition, general purpose vinyl acetate adhesives, ethylene vinyl acetate copolymer adhesives, acrylic resin adhesives, α-olefin adhesives, styrene-butadiene rubber latex adhesives, vinyl chloride resin adhesives, chloroprene adhesives, nitrile rubber adhesives, urethane rubber adhesives, and epoxy resins Adhesives, silicone resin adhesives, modified silicone adhesives, epoxy-modified silicone resin adhesives, silylated urethane resin adhesives, cyanoacrylate adhesives, and the like.

In this embodiment, you may use the organic resin which melt | dissolves in electrolyte solution, or dissolves and decomposes during electrolysis. The organic resin dissolved in the electrolyte or dissolved and decomposed during electrolysis is not limited to the following, but is not limited to, for example, vinyl acetate adhesive, ethylene vinyl acetate copolymer adhesive, acrylic resin adhesive, α-olefin adhesive, and styrene butadiene rubber latex. Adhesive, vinyl chloride resin adhesive, chloroprene adhesive, nitrile rubber adhesive, urethane rubber adhesive, epoxy adhesive, silicone resin adhesive, modified silicone adhesive, epoxy / modified silicone resin adhesive, silylated urethane resin adhesive, cyanoacrylate adhesive Etc. can be mentioned.

The fixed structure shown in FIG. 50 can be observed with an optical microscope or an electron microscope. In particular, after embedding the sample, a method of creating and observing a cross section by a microtome is preferable.

In this embodiment, it is preferable that at least one part of the fixing member grips the diaphragm and the electrode for electrolysis outside. This aspect is demonstrated using FIG. 51A.

The fixing structure shown in FIG. 51A is a structure in which the electrolytic electrode 2 and the diaphragm 3 are gripped from the outside and fixed. That is, between the outer surface 2b of the electrolytic electrode 2 and the outer surface 3b of the diaphragm 3 is clamped by the holding member as the fixing member 7, and is fixed. In the fixed structure shown in FIG. 51A, the state in which the holding member was dug into the electrolytic electrode 2 or the diaphragm 3 is also included. As a holding member, a tape, a clip, etc. are mentioned, for example.

In this embodiment, you may use the holding member melt | dissolved in electrolyte solution. As a holding member melt | dissolved in electrolyte solution, the tape made from PET, a clip, the tape made from PVA, a clip, etc. are mentioned, for example.

In contrast to FIGS. 47 to 50, the fixed structure shown in FIG. 51A does not bond the interface between the electrode 2 for electrolysis and the membrane 3, but each inner surface of the electrode 2 and the membrane 3 for electrolysis. (2a, 3a) are only in a contact or facing state, and by removing the holding member, the fixed state of the electrolytic electrode 2 and the diaphragm 3 can be released and separated.

Although not shown in FIG. 51A, the electrolytic electrode 2 and the diaphragm 3 may be fixed to the electrolytic cell by using a holding member.

For example, a PTFE-made tape can be folded back to fix the diaphragm and the electrode.

Moreover, in this embodiment, it is preferable that at least one part of the fixing member fixes the diaphragm and the electrode for electrolysis by magnetic force. This aspect is demonstrated using FIG. 51B.

The fixed structure shown in FIG. 51B is a structure in which the electrolytic electrode 2 and the diaphragm 3 are gripped and fixed from the outside. The difference from FIG. 51A is that a pair of magnets are used as the holding member as the fixing member. In the aspect of the fixing structure shown in FIG. 51B, after the laminate 1 is attached to the electrolytic cell, the holding member may be left as it is at the time of the electrolytic cell operation, or may be removed from the laminate 1.

Although not shown in FIG. 51B, the electrolytic electrode 2 and the diaphragm 3 may be fixed to the electrolytic cell by using a holding member. In addition, when a magnetic material that adheres to a magnet to a part of the material of the electrolytic cell is used, one gripping material is provided on the diaphragm surface side, and the electrolytic cell, the electrolytic electrode 2 and the diaphragm 3 are sandwiched therebetween. It can also be fixed.

In addition, a plurality of lines may be provided in the fixed area. That is, 1, 2, 3,... Toward the inner side from the contour side of the laminate 1. n fixed areas can be arranged. n is an integer of 1 or more. The m-th (m <n) fixed region and the L-th (m <L≤n) fixed region can be formed in different fixing patterns.

As for the fixed area | region formed in an electricity supply part, the shape of linear symmetry is preferable. There exists a tendency which can suppress stress concentration by this. For example, when two orthogonal directions are made into the X direction and the Y direction, a fixed area can be configured by arranging one in each of the X direction and the Y direction or a plurality of them in the X direction and the Y direction at equal intervals. Although the number of fixed areas in the X direction and the Y direction is not limited, it is preferable to be 100 or less in the X direction and the Y direction, respectively. In addition, from the viewpoint of securing the surface area of the energizing portion, the number of the fixed regions in the X direction and the Y direction is preferably 50 or less, respectively.

In the fixed area in the present embodiment, when the fixed structure shown in Figs. 47A and 49 is used, it is preferable to apply a sealing material on the film surface of the fixed area from the viewpoint of preventing short circuit caused by contact between the positive electrode and the negative electrode. Do. As a sealing material, the raw material demonstrated by the said adhesive agent can be used, for example.

When using the fixing member, when the area S3 and the area S3 'are obtained, the overlapping portion is not counted as the area S3 and the area S3' when the area for the fixing member overlaps. For example, when fixing the above-mentioned PTFE yarn as a fixing member, the portions where the PTFE yarns intersect do not count as overlapping areas. In addition, when fixing the above-mentioned PTFE tape as a fixing member, the part which overlaps PTFE tape does not count as an area as an overlap.

In addition, when the above-mentioned PTFE yarn or adhesive agent is fixed as a fixing member, the area existing on the back surface of the electrolytic electrode and / or the diaphragm is also counted as area S3 and area S3 '.

As described above, the laminate in the present embodiment may have various fixed regions at various positions. In particular, the electrolytic electrode is added to the aforementioned electrode in a portion where the fixed region does not exist (non-fixed region). Power ”is desirable. That is, it is preferable that the force applied per unit mass and unit area in the non-fixed region of the electrolytic electrode is less than 1.5 N / mg · cm 2.

[Electrolysis tank]

The electrolytic cell of this embodiment contains the laminated body of this embodiment. EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of an electrolytic cell is explained in full detail, for example, when salt electrolysis is performed using an ion exchange membrane as a diaphragm.

[Electrolysis cell]

52 is a cross-sectional view of the electrolytic cell 1.

The electrolytic cell 1 includes the anode chamber 10, the cathode chamber 20, the partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, and the anode provided in the anode chamber 10. 11 and a cathode 21 provided in the cathode chamber 20. If necessary, the base 18a and the reverse current absorbing layer 18b formed on the base 18a may be provided, and the reverse current absorber 18 provided in the cathode chamber may be provided. The positive electrode 11 and the negative electrode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 has the following cathode structure. The negative electrode structure 40 includes a negative electrode chamber 20, a negative electrode 21 provided in the negative electrode chamber 20, and a reverse current absorber 18 provided in the negative electrode chamber 20, and the reverse current absorber 18. 56 has a base 18a and a reverse current absorbing layer 18b formed on the base 18a, and the cathode 21 and the reverse current absorbing layer 18b are electrically connected to each other. The negative electrode chamber 20 further includes a current collector 23, a support 24 supporting the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the electrical power collector 23 and the negative electrode 21. The support body 24 is provided between the collector 23 and the partition 30. The current collector 23 is electrically connected to the negative electrode 21 via the metal elastic body 22. The partition 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition 30, the support body 24, the collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected to each other. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be connected indirectly via a current collector, a support, a metal elastic body, a partition, or the like. It is preferable that the whole surface of the cathode 21 is covered with a catalyst layer for the reduction reaction. In addition, in the form of electrical connection, the partition 30 and the support body 24, the support body 24 and the collector 23, the collector 23 and the metal elastic body 22 are respectively directly attached, and the metal elastic body 22 ) May be laminated on the cathode 21. Welding etc. are mentioned as a method of attaching these structural members directly to each other. In addition, the reverse current absorber 18, the negative electrode 21, and the current collector 23 may be collectively referred to as the negative electrode structure 40.

53 is a cross-sectional view of two electrolytic cells 1 adjacent in the electrolytic cell 4. 54 shows the electrolytic cell 4. 55 shows a step of assembling the electrolytic cell 4. As shown in FIG. 53, the electrolysis cell 1, the cation exchange membrane 2, and the electrolysis cell 1 are arranged in series in this order. The ion exchange membrane 2 is arrange | positioned between the anode chamber of one electrolytic cell 1 and the cathode chamber of the other electrolytic cell 1 among two electrolytic cells which adjoin in an electrolytic cell. In other words, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are spaced apart by the cation exchange membrane 2. As shown in FIG. 54, the electrolytic cell 4 is composed of a plurality of electrolytic cells 1 connected in series via an ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 55, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series via an ion exchange membrane 2 and being connected by a press 5.

The electrolytic cell 4 has the positive terminal 7 and the negative terminal 6 connected to a power supply. The positive electrode 11 of the electrolytic cell 1 positioned at the shortest of the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4 is electrically connected to the positive electrode terminal 7. Among the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4, the negative electrode 21 of the electrolytic cell located at the end opposite to the positive electrode terminal 7 is electrically connected to the negative electrode terminal 6. The electric current at the time of electrolysis flows toward the negative electrode terminal 6 from the positive terminal 7 side via the positive electrode and the negative electrode of each electrolytic cell 1. Moreover, you may arrange | position the electrolytic cell (anode terminal cell) which has only an anode chamber, and the electrolytic cell (cathode terminal cell) which has only a cathode chamber in the both ends of the electrolytic cell 1 which connected. In this case, the positive terminal 7 is connected to the positive terminal cell disposed at one end thereof, and the negative terminal 6 is connected to the negative terminal cell arranged at the other end thereof.

In the case of electrolysis of brine, brine is supplied to each anode chamber 10, and pure or low concentration aqueous sodium hydroxide solution is supplied to the cathode chamber 20. Each liquid is supplied to each electrolytic cell 1 from electrolyte supply pipe (not shown) via electrolyte supply hose (not shown). In addition, electrolyte solution and the product by electrolysis are collect | recovered from an electrolyte collection pipe (not shown). In electrolysis, sodium ions in brine move from the anode chamber 10 of one electrolytic cell 1 through the ion exchange membrane 2 to the cathode chamber 20 of the neighboring electrolytic cell 1. Therefore, the current during electrolysis flows along the direction in which the electrolytic cells 1 are connected in series. That is, the current flows from the anode chamber 10 toward the cathode chamber 20 via the cation exchange membrane 2. By electrolysis of the brine, chlorine gas is produced on the anode 11 side, and sodium hydroxide (solute) and hydrogen gas are produced on the cathode 21 side.

(Positive room)

The anode chamber 10 includes a cathode 11 or an anode feeder 11. When the electrode for electrolysis in this embodiment is inserted in the anode side, 11 functions as a positive electrode feeder. When the electrode for electrolysis in this embodiment is not inserted in the anode side, 11 functions as an anode. In addition, the anode chamber 10 is disposed on an anode side electrolyte supply portion for supplying an electrolyte solution to the anode chamber 10 and an anode side electrolyte supply portion, and a baffle plate disposed to be substantially parallel or oblique with the partition wall 30. And it is preferable to have an anode side gas-liquid separation part arrange | positioned above the baffle plate and isolate | separates a gas from the electrolyte solution which gas mixed.

(anode)

When the electrode for electrolysis in this embodiment is not inserted in the anode side, the anode 11 is provided in the frame of the anode chamber 10. As the anode 11, a metal electrode such as so-called DSA (registered trademark) can be used. DSA is a titanium-based electrode whose surface was covered with an oxide containing ruthenium, iridium and titanium.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Positive electrode feeder)

When the electrode for electrolysis in this embodiment is inserted in the anode side, the positive electrode feeder 11 is provided in the frame of the anode chamber 10. As the positive electrode feeder 11, a metal electrode such as DSA (registered trademark) or the like may be used, or titanium without a catalyst coating may be used. It is also possible to use DSA with a thinner catalyst coating thickness. Moreover, the used anode can also be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Anode-side electrolyte supply unit)

The anode-side electrolyte supply unit supplies the electrolyte solution to the anode chamber 10 and is connected to the electrolyte solution supply pipe. It is preferable that an anode side electrolyte supply part is arrange | positioned under the anode chamber 10. As an anode side electrolyte supply part, the pipe (dispersion pipe) etc. which have an opening part formed in the surface can be used, for example. It is more preferable that such a pipe is arrange | positioned in parallel with the bottom part 19 of an electrolysis cell along the surface of the anode 11. This pipe is connected to the electrolyte supply pipe (liquid supply nozzle) which supplies electrolyte solution in the electrolysis cell 1. The electrolyte solution supplied from the liquid supply nozzle is conveyed to the electrolysis cell 1 by the pipe, and is supplied to the inside of the anode chamber 10 from the opening provided in the surface of the pipe. By arranging the pipes parallel to the bottom portion 19 of the electrolytic cell along the surface of the anode 11, the electrolyte can be uniformly supplied into the anode chamber 10, which is preferable.

(Positive side gas-liquid separator)

It is preferable that the anode-side gas-liquid separator is disposed above the baffle plate. During electrolysis, the anode-side gas-liquid separator has a function of separating the generated gas such as chlorine gas and the electrolyte. In addition, unless otherwise indicated, an upper side means the upward direction in the electrolysis cell 1 of FIG. 52, and a lower side means the downward direction in the electrolysis cell 1 of FIG.

At the time of electrolysis, when the generated gas and electrolyte generated in the electrolytic cell 1 become mixed phase (gas-liquid mixed phase) and discharged out of the system, vibration occurs due to pressure fluctuation inside the electrolytic cell 1, and physical damage of the ion exchange membrane is prevented. I may cause it. In order to suppress this, it is preferable that the positive electrode side gas-liquid separation part for separating a gas and a liquid is provided in the electrolysis cell 1 of this embodiment. It is preferable that a defoaming plate for removing bubbles is provided in the anode-side gas-liquid separator. When a gas-liquid mixture flows through a vesicle plate, a bubble bursts and can be isolate | separated into electrolyte solution and gas. As a result, vibration during electrolysis can be prevented.

(Baffle version)

It is preferable that the baffle plate is disposed above the anode-side electrolyte supply portion, and is disposed substantially parallel to or inclined with the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. By providing the baffle plate, the electrolyte solution (salt water, etc.) can be circulated internally in the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged to be spaced apart from the space near the anode 11 and the space near the partition wall 30. From this viewpoint, the baffle plate is preferably provided so as to face each surface of the anode 11 and the partition wall 30. In the space near the anode partitioned by the baffle plate, electrolytic solution concentration (saline concentration) decreases as electrolysis proceeds, and product gas such as chlorine gas is generated. Thereby, the specific gravity difference of gas-liquid arises in the space near the anode 11 divided by the baffle plate, and the space near the partition 30. As shown in FIG. By using this, the internal circulation of the electrolyte solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolyte solution in the anode chamber 10 can be made more uniform.

Although not shown in FIG. 52, a current collector may be separately provided inside the positive electrode chamber 10. As such an electrical power collector, it can also be set as the material and structure similar to the electrical power collector of the negative electrode chamber mentioned later. In the anode chamber 10, the anode 11 itself can also function as a current collector.

(septum)

The partition 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition 30 may be called a separator and divides the anode chamber 10 and the cathode chamber 20. As the partition 30, a well-known thing can be used as a separator for electrolysis, For example, the partition which welded the plate which consists of nickel to the cathode side, and titanium to the anode side, etc. are mentioned.

(Cathode room)

The cathode chamber 20 functions as a cathode feeder when the electrode for electrolysis in the present embodiment is inserted on the cathode side, and when the electrode for electrolyte in the present embodiment is not inserted on the cathode side. , 21 functions as a cathode. When the reverse current absorber is provided, the negative electrode or the negative electrode feeder 21 and the reverse current absorber are electrically connected to each other. In addition, it is preferable that the cathode chamber 20 also has a cathode side electrolyte solution supply section and a cathode side gas-liquid separation section similarly to the anode chamber 10. In addition, description is abbreviate | omitted about the same thing as each part which comprises the anode chamber 10 among each site | part which comprises the cathode chamber 20. As shown in FIG.

(cathode)

When the electrode for electrolysis in this embodiment is not inserted in the cathode side, the cathode 21 is provided in the frame of the cathode chamber 20. It is preferable that the negative electrode 21 has a catalyst layer which covers a nickel substrate and a nickel substrate. As a component of the catalyst layer on the nickel substrate, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd , Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho And metals such as Er, Tm, Yb and Lu, and oxides or hydroxides of the metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may give reduction process to the negative electrode 21 as needed. As the base material of the negative electrode 21, one in which nickel, nickel alloy, iron, or stainless steel is plated with nickel may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Cathode feeder)

When the electrode for electrolysis in this embodiment is inserted in the cathode side, the negative electrode feeder 21 is provided in the frame of the cathode chamber 20. The catalyst component may be coated on the negative electrode feeder 21. The catalyst component may be originally used as a negative electrode and remain. As components of the catalyst layer, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Metals, such as Tm, Yb, Lu, and the oxide or hydroxide of this metal are mentioned. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may use what plated nickel with nickel, nickel alloys, iron, or stainless steel which are not catalyst coated. As the base material of the negative electrode feeder 21, a plated nickel on nickel, a nickel alloy, iron or stainless may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

Reverse Current Absorption Layer

A material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected as the material of the reverse current absorbing layer. For example, nickel, iron, etc. are mentioned.

(Current collector)

The negative electrode chamber 20 preferably includes a current collector 23. This increases the current collecting effect. In the present embodiment, the current collector 23 is a porous plate, and is preferably disposed substantially parallel to the surface of the negative electrode 21.

The current collector 23 is preferably made of an electrically conductive metal such as nickel, iron, copper, silver, titanium, or the like. The current collector 23 may be a mixture of these metals, an alloy or a composite oxide. In addition, as long as it is a shape which functions as an electrical power collector, the shape of the electrical power collector 23 may be any shape, and plate-shaped or network-shaped may be sufficient as it.

(Metal elastomer)

By providing the metal elastic body 22 between the collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, The distance between each anode 11 and each cathode 21 can be shortened, and the voltage applied to the entire plurality of electrolytic cells 1 connected in series can be lowered. By lowering the voltage, the total consumption can be reduced. Moreover, when the metal elastic body 22 is provided and the laminated body containing the electrode for electrolysis which concerns on this embodiment is installed in an electrolytic cell, the said electrode for electrolysis by the pressure pressed by the metal elastic body 22 is carried out. Can be kept in a stable position.

As the metallic elastic body 22, a spring member, such as a spiral spring and a coil, a cushion mat, etc. can be used. As the metal elastic body 22, a suitable one can be appropriately adopted in consideration of a stress or the like which presses the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the collector 23 on the cathode chamber 20 side, or may be provided on the surface of the partition wall on the anode chamber 10 side. Usually, since both chambers are partitioned so that the cathode chamber 20 becomes smaller than the anode chamber 10, from the viewpoint of the strength of the frame or the like, the metal elastic body 22 is used for the current collector 23 of the cathode chamber 20. It is preferable to provide between and the cathode 21. Moreover, it is preferable that the metal elastic body 22 consists of metal which has electrical conductivity, such as nickel, iron, copper, silver, titanium.

(Support)

The negative electrode chamber 20 preferably includes a support 24 for electrically connecting the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently.

The support 24 is preferably made of a metal having electrical conductivity such as nickel, iron, copper, silver, titanium, or the like. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod, plate, or network. The support body 24 is plate-shaped, for example. The plurality of supports 24 are disposed between the partition wall 30 and the current collector 23. The plurality of supports 24 are arranged such that their respective surfaces are parallel to each other. The support body 24 is disposed substantially perpendicular to the partition wall 30 and the current collector 23.

(Anode side gasket, cathode side gasket)

It is preferable that the anode side gasket is arranged on the surface of the frame body constituting the anode chamber 10. It is preferable that the cathode side gasket is arrange | positioned at the surface of the frame body which comprises the cathode chamber 20. As shown in FIG. The anode side gasket of one electrolytic cell and the cathode side gasket of the electrolytic cell adjacent to this are connected so that the electrolytic cells may be pinched | interposed on the ion exchange membrane 2 (refer FIG. 52, 53). By these gaskets, when connecting a plurality of electrolytic cells 1 in series via the ion exchange membrane 2, airtightness can be provided to a connection location.

A gasket seals between an ion exchange membrane and an electrolysis cell. As a specific example of a gasket, a frame-shaped rubber sheet etc. in which the opening part was formed in the center are mentioned. The gasket is required to be resistant to corrosive electrolytes, generated gases and the like and to be used for a long time. Therefore, from the viewpoint of chemical resistance and hardness, vulcanized products, peroxide crosslinked products and the like of ethylene propylene diene rubber (EPDM rubber) and ethylene propylene rubber (EPM rubber) are usually used as the gasket. Moreover, the gasket which coat | covered the area | region (contact part) which contact | connects a liquid as needed with fluororesin, such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether polymer (PFA), can also be used. These gaskets should just have opening parts, respectively, so that the flow of electrolyte solution may not be disturbed, The shape is not specifically limited. For example, a frame-shaped gasket is bonded with an adhesive or the like along the circumferential edge of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20. For example, when connecting two electrolytic cells 1 via the ion exchange membrane 2 (refer FIG. 53), when each electrolytic cell 1 which bonded the gasket through the ion exchange membrane 2 is fastened, do. Thereby, it can suppress that an electrolyte solution, the alkali metal hydroxide produced by electrolysis, chlorine gas, hydrogen gas, etc. leak to the exterior of the electrolysis cell 1.

(Ion exchange membrane (2))

As the ion exchange membrane 2, it is as described in the term of the said ion exchange membrane.

(Hydraulic)

In the electrolytic cell of this embodiment, the electrolytic cell in the case of performing electrolytic electrolysis has the structure which changed the ion exchange membrane in the electrolytic cell in the case of performing the above-mentioned salt electrolysis to a microporous membrane. In addition, since the raw material to be supplied is water, it differs from the electrolytic cell in the case of performing the above-mentioned salt electrolysis. As for other configurations, the same configuration as the electrolytic cell in the case of performing salt electrolysis can also be adopted. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. However, in the case of hydrolysis, since oxygen gas is only generated in the anode chamber, the same material as the cathode chamber is used. Can be used. For example, nickel etc. can be mentioned. In addition, the anode coating is suitably a catalyst coating for oxygen generation. Examples of catalyst coatings include metals, oxides, hydroxides, and the like of platinum group metals and transition metals. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used.

Fourth Embodiment

Here, the 4th Embodiment of this invention is described in detail, referring FIGS. 63-90.

[Electrolyzer]

The electrolytic cell of the fourth embodiment (hereinafter simply referred to as "the present embodiment" in the term of <fourth embodiment>) includes an anode, an anode frame for supporting the anode, and an anode side disposed on the anode frame. As a laminate of a gasket, a negative electrode facing the positive electrode, a negative electrode frame supporting the negative electrode, a negative electrode side gasket disposed on the negative electrode frame and facing the positive electrode side gasket, a diaphragm and an electrode for electrolysis, A laminate disposed between the anode side gasket and the cathode side gasket, wherein at least a part of the laminate is sandwiched between the anode side gasket and the cathode side gasket, and the electrolytic electrode is 50 mm × 50. The airflow resistance in the case of a size of mm and a temperature of 24 ° C., a relative humidity of 32%, a piston speed of 0.2 cm / s, and an air flow rate of 0.4 cc / cm 2 / s is 24 kPa · s / m or less. Since it is comprised as mentioned above, the electrolytic cell of this embodiment is excellent in electrolytic performance and can prevent damage of a diaphragm.

The electrolytic cell of this embodiment includes the above-mentioned structural member, in other words, it contains an electrolytic cell. EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of an electrolytic cell is explained in full detail, for example, when salt electrolysis is performed using an ion exchange membrane as a diaphragm.

[Electrolysis cell]

First, the electrolytic cell which can be used as a structural unit of the electrolytic cell of this embodiment is demonstrated. 63 is a cross-sectional view of the electrolytic cell 1.

The electrolytic cell 1 includes the anode chamber 10, the cathode chamber 20, the partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, and the anode provided in the anode chamber 10. 11 and a cathode 21 provided in the cathode chamber 20. If necessary, the base 18a and the reverse current absorbing layer 18b formed on the base 18a may be provided, and the reverse current absorber 18 provided in the cathode chamber may be provided. The positive electrode 11 and the negative electrode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 has the following cathode structure. The negative electrode structure 40 includes a negative electrode chamber 20, a negative electrode 21 provided in the negative electrode chamber 20, and a reverse current absorber 18 provided in the negative electrode chamber 20, and the reverse current absorber 18. As shown in FIG. 67, the substrate 18a and the reverse current absorbing layer 18b formed on the substrate 18a are electrically connected to the cathode 21 and the reverse current absorbing layer 18b. The negative electrode chamber 20 further includes a current collector 23, a support 24 supporting the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the electrical power collector 23 and the negative electrode 21. The support body 24 is provided between the collector 23 and the partition 30. The current collector 23 is electrically connected to the negative electrode 21 via the metal elastic body 22. The partition 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition 30, the support body 24, the collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected to each other. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be connected indirectly via a current collector, a support, a metal elastic body, a partition, or the like. It is preferable that the whole surface of the cathode 21 is covered with a catalyst layer for the reduction reaction. In addition, in the form of electrical connection, the partition 30 and the support body 24, the support body 24 and the collector 23, the collector 23 and the metal elastic body 22 are respectively directly attached, and the metal elastic body 22 ) May be laminated on the cathode 21. Welding etc. are mentioned as a method of attaching these structural members directly to each other. In addition, the reverse current absorber 18, the negative electrode 21, and the current collector 23 may be collectively referred to as the negative electrode structure 40.

64 is a cross-sectional view of two electrolytic cells 1 adjacent in the electrolytic cell 4. 65 shows the electrolytic cell 4. 66 shows a step of assembling the electrolytic cell 4.

In the conventional electrolytic cell, as shown in FIG. 64A, the electrolytic cell 1, the diaphragm (here cation exchange membrane) 2, and the electrolytic cell 1 are arranged in this order in series, and two adjacent cells in the electrolyzer are arranged. The ion exchange membrane 2 is arrange | positioned between the anode chamber of one electrolytic cell 1 and the cathode chamber of the other electrolytic cell 1 among electrolytic cells. That is, in the electrolytic cell, normally, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent to this are spaced apart by the cation exchange membrane 2.

On the other hand, in this embodiment, as shown in FIG. 64B, the laminated body 25 which has the electrolysis cell 1, the diaphragm (here cation exchange membrane) 2, and the electrode for electrolysis (here, a cathode for update) 21a, The electrolytic cells 1 are arranged in series in this order, and the laminate 25 is sandwiched between the positive electrode gasket 12 and the negative electrode gasket 13 at a part thereof (upper end in FIG. 64B).

As shown in FIG. 65, the electrolytic cell 4 is composed of a plurality of electrolytic cells 1 connected in series via an ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 66, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series via the ion exchange membrane 2 and being connected by the press 5.

The electrolytic cell 4 has the positive terminal 7 and the negative terminal 6 connected to a power supply. The positive electrode 11 of the electrolytic cell 1 positioned at the shortest of the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4 is electrically connected to the positive electrode terminal 7. Among the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4, the negative electrode 21 of the electrolytic cell located at the end opposite to the positive electrode terminal 7 is electrically connected to the negative electrode terminal 6. The electric current at the time of electrolysis flows toward the negative electrode terminal 6 from the positive terminal 7 side via the positive electrode and the negative electrode of each electrolytic cell 1. Moreover, you may arrange | position the electrolytic cell (anode terminal cell) which has only an anode chamber, and the electrolytic cell (cathode terminal cell) which has only a cathode chamber in the both ends of the electrolytic cell 1 which connected. In this case, the positive terminal 7 is connected to the positive terminal cell disposed at one end thereof, and the negative terminal 6 is connected to the negative terminal cell arranged at the other end thereof.

In the case of electrolysis of brine, brine is supplied to each anode chamber 10, and pure or low concentration aqueous sodium hydroxide solution is supplied to the cathode chamber 20. Each liquid is supplied to each electrolytic cell 1 from electrolyte supply pipe (not shown) via electrolyte supply hose (not shown). In addition, electrolyte solution and the product by electrolysis are collect | recovered from an electrolyte collection pipe (not shown). In electrolysis, sodium ions in brine move from the anode chamber 10 of one electrolytic cell 1 through the ion exchange membrane 2 to the cathode chamber 20 of the neighboring electrolytic cell 1. Therefore, the current during electrolysis flows along the direction in which the electrolytic cells 1 are connected in series. That is, the current flows from the anode chamber 10 toward the cathode chamber 20 via the cation exchange membrane 2. By electrolysis of the brine, chlorine gas is produced on the anode 11 side, and sodium hydroxide (solute) and hydrogen gas are produced on the cathode 21 side.

As described above, when the diaphragm, the negative electrode, and the positive electrode in the electrolytic cell are normally degraded in accordance with the operation of the electrolytic cell, and eventually need to be replaced with a new one, only the diaphragm is replaced. Although it can be simply updated by taking out a new diaphragm and inserting a new diaphragm, when the anode or cathode is exchanged by welding, it is complicated because a dedicated facility is required.

On the other hand, in the present embodiment, as described above, the laminate 25 is sandwiched between the positive electrode gasket 12 and the negative electrode gasket 13 at a part thereof (the upper end portion in FIG. 64B). In particular, in the example shown in FIG. 64B, the diaphragm (here, the cation exchange membrane) 2 and the electrolytic electrode (here, the update cathode) 21a are formed from the anode gasket 12 from the anode gasket 12 at least at the upper end of the laminate 25. It can fix by pressurization in the direction which goes to the direction, and pressurization in the direction toward the laminated body 25 from the negative electrode gasket 13. In this case, since the laminated body 25 (especially an electrode for electrolysis) does not need to be fixed by welding with respect to an existing member (for example, an existing cathode), it is preferable. That is, when both the electrode for electrolysis and a diaphragm are pinched by the anode side gasket and the said cathode side gasket, since it exists in the tendency to improve the work efficiency at the time of electrode update in an electrolytic cell, it is preferable.

Moreover, according to the structure of the electrolytic cell of this embodiment, since the diaphragm and the electrode for electrolysis are fully fixed as a laminated body, the outstanding electrolytic performance can be obtained.

(Positive room)

The anode chamber 10 includes a cathode 11 or an anode feeder 11. The term "feeder" as used herein means a deteriorated electrode (that is, an existing electrode), an electrode not coated with a catalyst, or the like. When the electrode for electrolysis in this embodiment is inserted in the anode side, 11 functions as a positive electrode feeder. When the electrode for electrolysis in this embodiment is not inserted in the anode side, 11 functions as an anode. In addition, the anode chamber 10 is disposed on an anode side electrolyte supply portion for supplying an electrolyte solution to the anode chamber 10 and an anode side electrolyte supply portion, and a baffle plate disposed to be substantially parallel or oblique with the partition wall 30. And it is preferable to have an anode side gas-liquid separation part arrange | positioned above the baffle plate and isolate | separates a gas from the electrolyte solution which gas mixed.

(anode)

When the electrode for electrolysis in this embodiment is not inserted in the anode side, the anode 11 is provided in the frame (namely, anode frame) of the anode chamber 10. As the anode 11, a metal electrode such as so-called DSA (registered trademark) can be used. DSA is a titanium-based electrode whose surface was covered with an oxide containing ruthenium, iridium and titanium.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Positive electrode feeder)

When the electrode for electrolysis in this embodiment is inserted in the anode side, the positive electrode feeder 11 is provided in the frame of the anode chamber 10. As the positive electrode feeder 11, a metal electrode such as DSA (registered trademark) or the like may be used, or titanium without a catalyst coating may be used. It is also possible to use DSA with a thinner catalyst coating thickness. Moreover, the used anode can also be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Anode-side electrolyte supply unit)

The anode-side electrolyte supply unit supplies the electrolyte solution to the anode chamber 10 and is connected to the electrolyte solution supply pipe. It is preferable that an anode side electrolyte supply part is arrange | positioned under the anode chamber 10. As an anode side electrolyte supply part, the pipe (dispersion pipe) etc. which have an opening part formed in the surface can be used, for example. It is more preferable that such a pipe is arrange | positioned in parallel with the bottom part 19 of an electrolysis cell along the surface of the anode 11. This pipe is connected to the electrolyte supply pipe (liquid supply nozzle) which supplies electrolyte solution in the electrolysis cell 1. The electrolyte solution supplied from the liquid supply nozzle is conveyed to the electrolysis cell 1 by the pipe, and is supplied to the inside of the anode chamber 10 from the opening provided in the surface of the pipe. By arranging the pipes parallel to the bottom portion 19 of the electrolytic cell along the surface of the anode 11, the electrolyte can be uniformly supplied into the anode chamber 10, which is preferable.

(Positive side gas-liquid separator)

It is preferable that the anode-side gas-liquid separator is disposed above the baffle plate. During electrolysis, the anode-side gas-liquid separator has a function of separating the generated gas such as chlorine gas and the electrolyte. In addition, unless otherwise indicated, an upper side means the upward direction in the electrolysis cell 1 of FIG. 63, and a lower side means the downward direction in the electrolysis cell 1 of FIG.

At the time of electrolysis, when the generated gas and electrolyte generated in the electrolytic cell 1 become mixed phase (gas-liquid mixed phase) and discharged out of the system, vibration occurs due to pressure fluctuation inside the electrolytic cell 1, and physical damage of the ion exchange membrane is prevented. I may cause it. In order to suppress this, it is preferable that the positive electrode side gas-liquid separation part for separating a gas and a liquid is provided in the electrolysis cell 1 of this embodiment. It is preferable that a defoaming plate for removing bubbles is provided in the anode-side gas-liquid separator. When a gas-liquid mixture flows through a vesicle plate, a bubble bursts and can be isolate | separated into electrolyte solution and gas. As a result, vibration during electrolysis can be prevented.

(Baffle version)

It is preferable that the baffle plate is disposed above the anode-side electrolyte supply portion, and is disposed substantially parallel to or inclined with the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. By providing the baffle plate, the electrolyte solution (salt water, etc.) can be circulated internally in the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged to be spaced apart from the space near the anode 11 and the space near the partition wall 30. From this viewpoint, the baffle plate is preferably provided so as to face each surface of the anode 11 and the partition wall 30. In the space near the anode partitioned by the baffle plate, electrolytic solution concentration (saline concentration) decreases as electrolysis proceeds, and product gas such as chlorine gas is generated. Thereby, the specific gravity difference of gas-liquid arises in the space near the anode 11 divided by the baffle plate, and the space near the partition 30. As shown in FIG. By using this, the internal circulation of the electrolyte solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolyte solution in the anode chamber 10 can be made more uniform.

Although not shown in FIG. 63, a current collector may be separately provided inside the positive electrode chamber 10. As such an electrical power collector, it can also be set as the material and structure similar to the electrical power collector of the negative electrode chamber mentioned later. In the anode chamber 10, the anode 11 itself can also function as a current collector.

(septum)

The partition 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition 30 may be called a separator and divides the anode chamber 10 and the cathode chamber 20. As the partition 30, a well-known thing can be used as a separator for electrolysis, For example, the partition which welded the plate which consists of nickel to the cathode side, and titanium to the anode side, etc. are mentioned.

(Cathode room)

The cathode chamber 20 functions as a cathode feeder when the electrode for electrolysis in the present embodiment is inserted on the cathode side, and when the electrode for electrolyte in the present embodiment is not inserted on the cathode side. , 21 functions as a cathode. When the reverse current absorber is provided, the negative electrode or the negative electrode feeder 21 and the reverse current absorber are electrically connected to each other. In addition, it is preferable that the cathode chamber 20 also has a cathode side electrolyte solution supply section and a cathode side gas-liquid separation section similarly to the anode chamber 10. In addition, description is abbreviate | omitted about the same thing as each part which comprises the anode chamber 10 among each site | part which comprises the cathode chamber 20. As shown in FIG.

(cathode)

When the electrode for electrolysis in this embodiment is not inserted in the cathode side, the cathode 21 is provided in the frame (namely, the cathode frame) of the cathode chamber 20. It is preferable that the negative electrode 21 has a catalyst layer which covers a nickel substrate and a nickel substrate. As a component of the catalyst layer on the nickel substrate, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd , Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho And metals such as Er, Tm, Yb and Lu, and oxides or hydroxides of the metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may give reduction process to the negative electrode 21 as needed. As the base material of the negative electrode 21, one in which nickel, nickel alloy, iron, or stainless steel is plated with nickel may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Cathode feeder)

When the electrode for electrolysis in this embodiment is inserted in the cathode side, the negative electrode feeder 21 is provided in the frame of the cathode chamber 20. The catalyst component may be coated on the negative electrode feeder 21. The catalyst component may be originally used as a negative electrode and remain. As components of the catalyst layer, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Metals, such as Tm, Yb, Lu, and the oxide or hydroxide of this metal are mentioned. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may use what plated nickel with nickel, nickel alloys, iron, or stainless steel which are not catalyst coated. As the base material of the negative electrode feeder 21, a plated nickel on nickel, a nickel alloy, iron or stainless may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

Reverse Current Absorption Layer

A material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected as the material of the reverse current absorbing layer. For example, nickel, iron, etc. are mentioned.

(Current collector)

The negative electrode chamber 20 preferably includes a current collector 23. This increases the current collecting effect. In the present embodiment, the current collector 23 is a porous plate, and is preferably disposed substantially parallel to the surface of the negative electrode 21.

The current collector 23 is preferably made of an electrically conductive metal such as nickel, iron, copper, silver, titanium, or the like. The current collector 23 may be a mixture of these metals, an alloy or a composite oxide. In addition, as long as it is a shape which functions as an electrical power collector, the shape of the electrical power collector 23 may be any shape, and plate-shaped or network-shaped may be sufficient as it.

(Metal elastomer)

By providing the metal elastic body 22 between the collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, The distance between each anode 11 and each cathode 21 can be shortened, and the voltage applied to the entire plurality of electrolytic cells 1 connected in series can be lowered. By lowering the voltage, the total consumption can be reduced. Moreover, when the metal elastic body 22 is provided and the laminated body containing the electrode for electrolysis in this embodiment is installed in an electrolytic cell, the said electrode for electrolysis by the pressure pressed by the metal elastic body 22 is carried out. Can be kept in a stable position.

As the metallic elastic body 22, a spring member, such as a spiral spring and a coil, a cushion mat, etc. can be used. As the metal elastic body 22, a suitable one can be appropriately adopted in consideration of a stress or the like which presses the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the collector 23 on the cathode chamber 20 side, or may be provided on the surface of the partition wall on the anode chamber 10 side. Usually, since both chambers are partitioned so that the cathode chamber 20 becomes smaller than the anode chamber 10, from the viewpoint of the strength of the frame or the like, the metal elastic body 22 is used for the current collector 23 of the cathode chamber 20. It is preferable to provide between and the cathode 21. Moreover, it is preferable that the metal elastic body 22 consists of metal which has electrical conductivity, such as nickel, iron, copper, silver, titanium.

(Support)

The negative electrode chamber 20 preferably includes a support 24 for electrically connecting the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently.

The support 24 is preferably made of a metal having electrical conductivity such as nickel, iron, copper, silver, titanium, or the like. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod, plate, or network. The support body 24 is plate-shaped, for example. The plurality of supports 24 are disposed between the partition wall 30 and the current collector 23. The plurality of supports 24 are arranged such that their respective surfaces are parallel to each other. The support body 24 is disposed substantially perpendicular to the partition wall 30 and the current collector 23.

(Anode side gasket, cathode side gasket)

It is preferable that the anode side gasket is arranged on the surface of the frame body constituting the anode chamber 10. It is preferable that the cathode side gasket is arrange | positioned at the surface of the frame body which comprises the cathode chamber 20. As shown in FIG. The electrolytic cells are connected so that the anode side gasket which one electrolytic cell is equipped, and the cathode side gasket of the electrolysis cell adjacent to this clamp the laminated body 25 (refer FIG. 64B). By these gaskets, when connecting the some electrolytic cell 1 in series via the laminated body 25, airtightness can be provided to a connection location.

A gasket seals between an ion exchange membrane and an electrolysis cell. As a specific example of a gasket, a frame-shaped rubber sheet etc. in which the opening part was formed in the center are mentioned. The gasket is required to be resistant to corrosive electrolytes, generated gases and the like and to be used for a long time. Therefore, from the viewpoint of chemical resistance and hardness, vulcanized products, peroxide crosslinked products and the like of ethylene propylene diene rubber (EPDM rubber) and ethylene propylene rubber (EPM rubber) are usually used as the gasket. Moreover, the gasket which coat | covered the area | region (contact part) which contact | connects a liquid as needed with fluororesin, such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether polymer (PFA), can also be used. These gaskets should just have openings, so that the flow of electrolyte solution may not be disturbed, and the shape is not specifically limited. For example, a frame-shaped gasket is bonded with an adhesive or the like along the circumferential edge of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20. By sandwiching the laminated body 25 with the positive electrode gasket and the negative electrode gasket, leakage of the electrolyte solution, alkali metal hydroxide, chlorine gas, hydrogen gas, etc. generated by electrolysis can be suppressed to the outside of the electrolytic cell 1.

[Laminated body]

The laminate in this embodiment has a membrane and an electrode for electrolysis. The laminated body in this embodiment can improve the work efficiency at the time of electrode update in an electrolytic cell, and can express the outstanding electrolytic performance after an update. That is, when the electrode is updated by the laminate in the present embodiment, the electrode can be updated by a simple operation such as updating the diaphragm without involving complicated operations such as peeling off an existing electrode fixed to the electrolytic cell. As a result, the work efficiency is greatly improved.

Moreover, according to the laminated body in this embodiment, the electrolytic performance of the existing electrolytic cell can be maintained or improved equivalent to the performance at the time of a new article. Therefore, the electrode which is fixed to the existing electrolytic cell and functions as a positive electrode and a negative electrode only needs to function as a feeder, and the catalyst coating can be greatly reduced or zero.

[Electrode Electrode]

The electrolytic electrode in this embodiment makes the electrolytic electrode 50 mm x 50 mm in size, and has a temperature of 24 degreeC, a relative humidity of 32%, a piston speed of 0.2 cm / s, and an airflow of 0.4 cc / cm <2> / s. In one case (hereinafter, also referred to as "measurement condition 1"), the ventilation resistance (hereinafter, also referred to as "ventilation resistance 1") is 24 kPa · s / m or less. High ventilation resistance means that air is difficult to flow, and indicates a high density. In this state, the electrolytic product remains in the electrode and the reaction substrate becomes less likely to diffuse into the electrode, resulting in poor electrolytic performance (voltage, etc.). In addition, the concentration of the film surface increases. Specifically, the caustic concentration increases on the cathode side, and the supplyability of brine decreases on the anode side. As a result, the product remains at a high concentration at the interface where the diaphragm and the electrode contact, leading to damage of the diaphragm, leading to voltage rise and film damage on the cathode surface and film damage on the anode surface. In this embodiment, in order to prevent such a problem, a ventilation resistance shall be 24 kPa * s / m or less.

In addition, in this embodiment, when the ventilation resistance is greater than or equal to a certain level, in the case of the negative electrode, NaOH generated at the electrode tends to remain at the interface between the electrode and the diaphragm, resulting in a high concentration. In order to prevent the damage to the diaphragm which may occur due to such retention, it is preferably less than 0.19 kPa · s / m, more preferably 0.15 kPa · s / m or less. And it is more preferable that it is 0.07 kPa * s / m or less.

On the other hand, when the airflow resistance is low, the area of the electrode becomes small, so that the current supply area becomes small and the electrolytic performance (voltage, etc.) deteriorates. In the case where the ventilation resistance is zero, since the electrode for electrolysis is not provided, a feeder functions as an electrode and electrolytic performance (voltage etc.) becomes remarkably bad. In this regard, the lower limit specified as the ventilation resistance 1 is not particularly limited, but is preferably more than 0 kPa · s / m, more preferably 0.0001 kPa · s / m or more, still more preferably 0.001 kPa S / m or more.

In addition, the ventilation resistance 1 may not be able to obtain sufficient measurement accuracy in 0.07 kPa * s / m or less on the measuring method. In view of this, for the electrode for electrolysis having a ventilation resistance 1 of 0.07 kPa · s / m or less, the ventilation resistance according to the following measuring method (hereinafter also referred to as “measurement condition 2”) (hereinafter also referred to as “airflow resistance 2”) Evaluation by is also possible. That is, the ventilation resistance 2 sets the electrode for electrolysis to the size of 50 mm x 50 mm, and it is the ventilation | emission when the temperature is 24 degreeC, the relative humidity 32%, the piston speed 2 cm / s, and the ventilation amount 4 cc / cm <2> / s. Resistance.

The measuring method of specific ventilation resistance 1 and 2 is as having described in the Example.

The ventilation resistances 1 and 2 can be in the above ranges by appropriately adjusting the porosity, electrode thickness, and the like described later, for example. More specifically, for example, when the pore rate is increased, the airflow resistances 1 and 2 tend to be small, and when the porosity is small, the airflow resistances 1 and 2 tend to be large.

The electrode for electrolysis in this embodiment can obtain favorable handling property, and is a unit from a viewpoint of having favorable adhesive force, such as a diaphragm, such as an ion exchange membrane and a microporous membrane, a feeder (a deteriorated electrode and a catalyst uncoated electrode), etc. The force applied per mass and unit area is preferably 1.6 N / (mg · cm 2) or less, more preferably less than 1.6 N / (mg · cm 2), still more preferably less than 1.5 N / (mg · cm 2) More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred.

From the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and even more preferably 0.1 N / mg · cm 2 or more. More preferably, it is 0.14 N / (mg * cm <2>) or more. 0.2 N / (mg * cm <2>) or more is more preferable from a viewpoint of the ease of handling in a large size (e.g., size 1.5 m x 2.5 m).

The said applied force can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, arithmetic mean surface roughness, etc., for example. More specifically, for example, when the porosity is increased, the applied force tends to be small, and when the porosity is decreased, the applied force tends to be large.

In addition, good handling properties can be obtained, good adhesion to diaphragms such as ion exchange membranes and microporous membranes, deteriorated electrodes, catalyst uncoated feeders and the like, and from the viewpoint of economy, the mass per unit area is 48 mg / cm 2 or less. It is preferable, More preferably, it is 30 mg / cm <2> or less, More preferably, it is 20 mg / cm <2> or less, It is preferable that it is 15 mg / cm <2> or less from a comprehensive viewpoint which combined handling property, adhesiveness, and economics. Although a lower limit is not specifically limited, For example, it is about 1 mg / cm <2>.

The said mass per unit area can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, etc., for example. More specifically, for example, if the thickness is the same, the mass per unit area tends to be smaller when the porosity is increased, and the mass per unit area tends to be larger when the porosity is reduced.

The force applied can be measured by the following method (i) or (ii) and is as having described in the Example in detail. The force applied is also referred to as the value obtained by the measurement of the method (i) (also referred to as "the applied force 1"), and the value obtained by the measurement of the method (ii) (also referred to as the "force 2 applied"). ) May be the same or different, but any value is preferably less than 1.5 N / mg · cm 2.

[Method (i)]

Nickel plate obtained by blasting with alumina of particle number 320 (thickness 1.2 mm, width 200 mm) and an ion exchange membrane coated with inorganic particles and a binder on both sides of a membrane of a perfluorocarbon polymer into which an ion exchanger was introduced (horizontal 170 mm in length and the details of the ion-exchange membrane here, as described in the Example) and an electrode sample (130 mm in length) were laminated in this order, and this laminated body was fully immersed in pure water, and then laminated body. A sample for measurement is obtained by removing excess moisture adhering to the surface. In addition, the arithmetic mean surface roughness Ra of the nickel plate after a blasting process is 0.5-0.8 micrometer. The specific calculation method of arithmetic mean surface roughness Ra is as having described in the Example.

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were raised in 10 mm in the vertical direction. Measure the weight when This measurement is performed three times to calculate an average value.

The average value is divided by the area of the overlapped portion of the electrode sample and the ion exchange membrane and the mass of the electrode sample of the overlapped portion with the ion exchange membrane, and the force applied per unit mass and unit area (1) (N / mg · cm 2) To calculate.

The force (1) applied per unit mass and unit area obtained by the method (i) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is preferable that it is 1.6 N / (mg * cm <2>) or less from a viewpoint of having more, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more and more preferably 0.14 N / (mg · cm 2) and 0.2 N / (mg · cm 2) from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m). ) Is more preferable.

[Method (ii)]

The nickel plate (thickness 1.2 mm, width 200 mm, the same nickel plate as the method (i)) and the electrode sample (length 130 mm) obtained by blasting with alumina of particle number 320 were laminated in this order. After fully immersing the laminate with pure water, a sample for measurement is obtained by removing excess moisture adhering to the laminate surface. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were 10 mm in the vertical direction. The weight at the time of rise is measured. This measurement is performed three times to calculate an average value.

This average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate, and the mass of the electrode sample in the overlapped portion of the nickel plate, and the adhesive force 2 per unit mass and unit area (N / mg · cm 2) is obtained. Calculate.

The force (2) applied per unit mass and unit area obtained by the method (ii) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is preferable that it is 1.6 N / (mg * cm <2>) or less from a viewpoint of having more, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more, and even more preferably, from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m), still more preferably 0.14 N / (mg · cm 2) or more.

It is preferable that the electrolytic electrode in this embodiment contains an electrolytic electrode base material and a catalyst layer. Although the thickness (gauge thickness) of the said electrolytic electrode base material is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feedstock), and an electrode without a catalyst coating (grade 300 micrometers or less are preferable from a viewpoint of having a good adhesive force with the whole), and being rolled suitably, being able to bend it favorably, and facilitating handling in a large size (e.g., size 1.5 m x 2.5 m). 205 micrometers or less are more preferable, 155 micrometers or less are more preferable, 135 micrometers or less are still more preferable, 125 micrometers or less are still more preferable, 120 micrometers or less are still more preferable, 100 micrometers or less are further more preferable In addition, from a viewpoint of handling property and economical efficiency, 50 micrometers or less are further more preferable. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), From the viewpoint of having good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and also in a large size (e.g., size 1.5 m x 2.5 m). It is more preferable that it is 95% or more from the viewpoint of easy handling. The upper limit is 100%.

[Method (2)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the condition of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 280 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), It is preferable that it is 75% or more, and it is more preferable that it is 80% or more from the viewpoint of having favorable adhesive force, and being able to wind up in roll shape suitably, and bend | bending favorably. It is more preferable that it is 90% or more from a viewpoint that handling at a size (for example, size 1.5 m x 2.5 m) becomes easy. The upper limit is 100%.

[Method (3)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 145 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

As for the electrode for electrolysis in this embodiment, it is preferable that the value measured by the following method (A) is 40 mm or less from a viewpoint of handling property, More preferably, it is 29 mm or less, More preferably, 19 mm It is as follows.

[Method (A)]

An ion exchange membrane (170 mm in width and length of the ion exchange membrane referred to herein) is coated with inorganic particles and a binder on both sides of a membrane of a perfluorocarbon polymer in which an ion exchanger is introduced under conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%. For details, as described in Examples) and the sample of the electrolytic electrode laminated, the electrolytic electrode was wound up and fixed on a curved surface of a vinyl chloride core material having an outer diameter of φ32 mm, and left standing for 6 hours. When separated and placed on a horizontal plate, the heights L ₁ and L ₂ in the vertical direction at both ends of the electrolytic electrode are measured, and these average values are measured.

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), It is preferable that it has a favorable adhesive force and is a porous structure from a viewpoint of the prevention of the residence of the gas which arises during electrolysis, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80% or less, still more preferably 20 to 75%.

In addition, an opening ratio is a ratio of an opening part per unit volume. The calculation method varies depending on whether the opening is also considered to submicron order or only the visible opening. In this embodiment, the volume V was calculated from the values of the gauge thickness, the width, and the length of the electrode, and the weight W was measured, and the porosity A was calculated by the following formula.

A = (1- (W / (V × ρ)) × 100

ρ is the density (g / cm 3) of the material of the electrode. For example, nickel is 8.908 g / cm 3 and titanium is 4.506 g / cm 3. The adjustment of the porosity is to change the area punching the metal per unit area if the punching metal, change the SW (short diameter), LW (long diameter), the feeding value if the expanded metal, the mesh diameter of the metal fiber, By changing the number of meshes, changing the pattern of the photoresist to be used for electroforming, changing the metal fiber diameter and fiber density for nonwoven fabrics, and changing the mold for forming the voids for the foamed metal, etc. I can adjust it.

EMBODIMENT OF THE INVENTION Hereinafter, one form of the electrode for electrolysis in this embodiment is demonstrated.

It is preferable that the electrolytic electrode which concerns on this embodiment contains an electrolytic electrode base material and a catalyst layer. The catalyst layer may be composed of a plurality of layers as described below or may have a single layer structure.

As shown in FIG. 68, the electrolytic electrode 100 according to the present embodiment includes a pair of first layers 20 covering both surfaces of the electrolytic electrode substrate 10 and the electrolytic electrode substrate 10. It is provided. It is preferable that the 1st layer 20 coat | covers the electrolytic electrode base material 10 whole. As a result, the catalytic activity and durability of the electrode for electrolysis tends to be improved. In addition, the first layer 20 may be laminated only on one surface of the electrode base 10 for electrolysis.

In addition, as shown in FIG. 68, the surface of the first layer 20 may be covered with the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, only one surface of the first layer 20 may be laminated on the second layer 30.

(Electrode base for electrolysis)

The electrolytic electrode substrate 10 is not particularly limited, but a valve metal such as nickel, nickel alloy, stainless steel or titanium may be used, and at least one selected from nickel (Ni) and titanium (Ti) may be used. It is preferable to include the element of a species.

When stainless steel is used in a high concentration aqueous alkali solution, considering that iron and chromium are eluted, and that the electrical conductivity of stainless steel is about 1/10 of nickel, the electrolytic electrode substrate includes nickel (Ni). The substrate is preferred.

In addition, when the electrolytic electrode base material 10 is used in the chlorine gas generation | occurence atmosphere in the high concentration saline solution near saturation, it is preferable that a material is titanium with high corrosion resistance.

There is no restriction | limiting in particular in the shape of the electrode base material 10 for electrolysis, An appropriate shape can be selected according to the objective. As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used. Especially, a punching metal or an expanded metal is preferable. In addition, electroforming is a technique which manufactures a metal thin film of a precise pattern by combining photolithography and an electroplating method. It is a method of pattern-forming with a photoresist on a board | substrate, electroplating to the part which is not protected by a resist, and obtaining metal foil.

The shape of the electrode base material for electrolysis has suitable specifications depending on the distance between the anode and the cathode in the electrolytic cell. Although not particularly limited, in the case where the anode and the cathode have a finite distance, an expanded metal or a punched metal shape can be used, and in the case of a so-called zero gap electrolytic cell in which the ion exchange membrane and the electrode are in contact, a woven mesh woven with fine lines , Wire mesh, foamed metal, metal nonwoven fabric, expanded metal, punched metal, metal porous foil and the like can be used.

Examples of the electrode base 10 for electrolysis include a metal porous foil, a wire mesh, a metal nonwoven fabric, a punching metal, an expanded metal or a foamed metal.

As a board | plate material before processing with a punching metal and an expanded metal, the board | plate material roll-molded, electrolytic foil, etc. are preferable. It is preferable that the electrolytic foil is further plated with the same element as the base material as post-treatment to form irregularities on one or both surfaces.

In addition, it is preferable that the thickness of the electrolytic electrode base material 10 is 300 micrometers or less as mentioned above, It is more preferable that it is 205 micrometers or less, It is more preferable that it is 155 micrometers or less, It is further more preferable that it is 135 micrometers or less, 125 It is still more preferable that it is micrometer or less, It is still more preferable that it is 120 micrometers or less, It is still more preferable that it is 100 micrometers or less, It is further more preferable that it is 50 micrometers or less from a viewpoint of handling property and economy. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In the electrode base for electrolysis, it is preferable to relieve the residual stress at the time of processing by annealing the electrode base for electrolysis in an oxidizing atmosphere. Moreover, in order to improve the adhesiveness with the catalyst layer coat | covered with the said surface, the surface of an electrolytic electrode base material uses unevenness | corrugation using a steel grid, alumina powder, etc., and it is preferable to increase a surface area by acid treatment after that. Do. Or it is preferable to plating by the same element as a base material, and to increase a surface area.

In order to make the surface of the 1st layer 20 and the electrode base material 10 for electrolysis adhere to the electrode base material 10 for electrolysis, it is preferable to perform the process which increases a surface area. Examples of the treatment for increasing the surface area include a blast treatment using a cut wire, a steel grid, an alumina grid, and the like, an acid treatment using sulfuric acid or hydrochloric acid, a plating treatment using the same element as the substrate, and the like. Although arithmetic mean surface roughness Ra of the surface of a base material is not specifically limited, 0.05 micrometer-50 micrometers are preferable, 0.1-10 micrometers is more preferable, 0.1-8 micrometers is still more preferable.

Next, the case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

In FIG. 68, the 1st layer 20 which is a catalyst layer contains at least 1 sort (s) of oxide of ruthenium oxide, iridium oxide, and titanium oxide. Of ruthenium oxide RuO _2, etc., it may be mentioned. IrO ₂ etc. are mentioned as an iridium oxide. Examples of titanium oxides include TiO ₂ . The first layer 20 preferably contains two kinds of oxides of ruthenium oxide and titanium oxide, or three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide. Thereby, the 1st layer 20 becomes a more stable layer, and also adhesiveness with the 2nd layer 30 improves more.

In the case where the first layer 20 includes two kinds of oxides of ruthenium oxide and titanium oxide, titanium contained in the first layer 20 with respect to one mole of ruthenium oxide included in the first layer 20. It is preferable that it is 1-9 mol, and, as for an oxide, it is more preferable that it is 1-4 mol. By setting the composition ratio of the two kinds of oxides in this range, the electrolytic electrode 100 exhibits excellent durability.

When the first layer 20 includes three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide, the first layer 20 is included in the first layer 20 with respect to one mole of ruthenium oxide contained in the first layer 20. It is preferable that it is 0.2-3 mol, and, as for the iridium oxide used, it is more preferable that it is 0.3-2.5 mol. Moreover, it is preferable that it is 0.3-8 mol, and, as for 1 mol of titanium oxide contained in the 1st layer 20 with respect to 1 mol of ruthenium oxide contained in the 1st layer 20, it is more preferable. By making the composition ratio of three types of oxides into this range, the electrode 100 for electrolysis shows the outstanding durability.

When the 1st layer 20 contains at least 2 types of oxide chosen from a ruthenium oxide, an iridium oxide, and a titanium oxide, it is preferable that these oxides form a solid solution. By forming the oxide solid solution, the electrolytic electrode 100 exhibits excellent durability.

In addition to the above composition, as long as it contains at least one oxide of ruthenium oxide, iridium oxide and titanium oxide, those having various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like, referred to as DSA (registered trademark), may be used as the first layer 20.

The first layer 20 does not need to be a single layer, but may include a plurality of layers. For example, the first layer 20 may include a layer containing three kinds of oxides and a layer containing two kinds of oxides. 0.05-10 micrometers is preferable and, as for the thickness of the 1st layer 20, 0.1-8 micrometers is more preferable.

(2nd floor)

It is preferable that the 2nd layer 30 contains ruthenium and titanium. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

It is preferable that the 2nd layer 30 contains palladium oxide, the solid solution of palladium oxide, and platinum, or the alloy of palladium and platinum. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

The longer the longer the thickness of the second layer 30 can maintain the electrolytic performance, the thickness of the second layer 30 is preferably 0.05 to 3 m.

Next, the case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

As a component of the first layer 20 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal include at least one kind, the alloy containing the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide and the platinum group metal is platinum, palladium, rhodium, It is preferable to contain at least 1 type of platinum group metal among ruthenium and iridium.

As a platinum group metal, it is preferable to contain platinum.

It is preferable that a platinum group metal oxide contains ruthenium oxide.

It is preferable that a platinum group metal hydroxide contains a ruthenium hydroxide.

As a platinum group metal alloy, it is preferable to include the alloy of platinum, nickel, iron, and cobalt.

Moreover, it is preferable to contain the oxide or hydroxide of a lanthanoid element as a 2nd component as needed. As a result, the electrolytic electrode 100 exhibits excellent durability.

The oxide or hydroxide of the lanthanoid-based element preferably contains at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium.

Moreover, it is preferable to contain the oxide or hydroxide of a transition metal as a 3rd component as needed.

By adding the third component, the electrolytic electrode 100 exhibits more excellent durability and can reduce the electrolytic voltage.

Examples of preferred combinations include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + platinum + palladium Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium + Sulfur, Ruthenium + Lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + samarium + cobalt, ruthenium + samarium + gallium, ruthenium + samarium + gallium, ruthenium + Samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + Nickel + palladium, bag Gold + nickel + ruthenium, an alloy of platinum and nickel, an alloy of platinum and cobalt, an alloy of platinum and iron, and the like.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal are not included, the main component of the catalyst is preferably nickel element.

It is preferable to contain at least 1 sort (s) among nickel metal, oxide, and hydroxide.

You may add a transition metal as a 2nd component. As a 2nd component to add, it is preferable to contain at least 1 type of element among titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon.

As a preferable combination, nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, etc. are mentioned.

If necessary, an intermediate layer can be formed between the first layer 20 and the electrolytic electrode substrate 10. By providing the intermediate layer, the durability of the electrolytic electrode 100 can be improved.

As an intermediate | middle layer, what has affinity for both the 1st layer 20 and the electrode base material 10 for electrolysis is preferable. As the intermediate layer, nickel oxide, platinum group metal, platinum group metal oxide, and platinum group metal hydroxide are preferable. As an intermediate | middle layer, it can form by apply | coating and baking the solution containing the component which forms an intermediate | middle layer, and can also form a surface oxide layer by heat-processing a base material at 300-600 degreeC in air atmosphere. In addition, it can form by a well-known method, such as a thermal spraying method and an ion plating method.

(2nd floor)

As the components of the first layer 30 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included. Examples of preferred combinations of the elements included in the second layer include combinations exemplified in the first layer. The combination of a 1st layer and a 2nd layer may be a combination with the same composition, and a composition ratio differs, and the combination of a different composition may be sufficient as it.

As thickness of a catalyst layer, the sum total of the formed catalyst layer and the intermediate | middle layer has preferable 0.01 micrometer-20 micrometers. If it is 0.01 micrometer or more, it can fully function as a catalyst. If it is 20 micrometers or less, a strong catalyst layer can be formed with little fall-out from a base material. 0.05 micrometers-15 micrometers are more preferable. More preferably, they are 0.1 micrometer-10 micrometers. More preferably, they are 0.2 micrometer-8 micrometers.

As thickness of an electrode, ie, the thickness of the sum total of an electrolytic electrode base material and a catalyst layer, 315 micrometers or less are preferable, 220 micrometers or less are more preferable, 170 micrometers or less are more preferable from a viewpoint of handling property of an electrode, 150 The thickness is even more preferable, 145 µm or less is particularly preferable, 140 µm or less is still more preferable, 138 µm or less is even more preferable, and 135 µm or less is even more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, it is preferable that it is 130 micrometers or less from a viewpoint similar to the above, More preferably, it is less than 130 micrometers, More preferably, it is 115 micrometers or less, More preferably, it is 65 micrometers or less. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, the thickness of an electrode can be calculated | required by measuring with a dejimatic thickness gauge (Mitsutoyo Corporation, minimum display 0.001 mm). The thickness of the electrode base material for electrodes is measured similarly to electrode thickness. The catalyst layer thickness can be obtained by subtracting the thickness of the electrode base material for electrolysis from the electrode thickness.

In the present embodiment, from the viewpoint of securing sufficient electrolytic performance, the electrode for electrolysis is Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y , Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd It is preferred to include at least one catalyst component selected from the group consisting of Pm, Sm, Eu, Gd, Tb and Dy.

In the present embodiment, the electrode for electrolysis can obtain better handling property as long as it is an electrode having a large elastic deformation region, and has better adhesion force such as a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, a catalyst-free feeder, and the like. From the viewpoint of having a thickness, the thickness of the electrode for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, still more preferably 170 µm or less, even more preferably 150 µm or less, and particularly 145 µm or less. Preferably, 140 micrometers or less are further more preferable, 138 micrometers or less are further more preferable, 135 micrometers or less are further more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, from a viewpoint similar to the above, 130 micrometers or less are preferable, less than 130 micrometers are more preferable, 115 micrometers or less are more preferable, and 65 micrometers or less are still more preferable. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, in this embodiment, a "elastic deformation area | region is wide" means that it is difficult to produce the curvature resulting from winding after winding an electrode for electrolysis to make a winding body, and canceling a wound state. In addition, the thickness of an electrode for electrolysis means the thickness which combined the electrode base material for electrolysis and a catalyst layer, when including the catalyst layer mentioned later.

(Method for producing electrode for electrolysis)

Next, one Embodiment of the manufacturing method of the electrolytic electrode 100 is described in detail.

In the present embodiment, the first layer 20, preferably the second layer (on the electrode base material for electrolysis) is performed by a method such as baking (pyrolysis) of the coating film in an oxygen atmosphere or ion plating, plating, thermal spraying or the like. By forming 30), the electrode 100 for electrolysis can be manufactured. In this manufacturing method of the present embodiment, high productivity of the electrode 100 for electrolysis can be realized. Specifically, a catalyst layer is formed on the electrode base material for electrolysis by a coating step of applying a coating liquid containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing pyrolysis. Pyrolysis means here that the metal salt used as a precursor is heated and decomposed | disassembled into a metal or metal oxide and gaseous substance. Although decomposition products differ depending on the metal species used, the kind of salt, and the atmosphere in which pyrolysis is performed, most metals tend to form oxides in an oxidizing atmosphere. In the industrial production process of electrodes, pyrolysis is usually carried out in air, and in most cases metal oxides or metal hydroxides are formed.

(Formation of the first layer of the anode)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved at least 1 sort (s) of metal salt of ruthenium, iridium, and titanium to an electrolytic electrode base material, and thermally decomposes (baking) in presence of oxygen. The content of ruthenium, iridium and titanium in the first coating liquid is approximately the same as that of the first layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of the second layer)

The 2nd layer 30 is formed as needed, for example, apply | coating the solution containing a palladium compound and a platinum compound, or the solution (2nd coating liquid) containing a ruthenium compound and a titanium compound on the 1st layer 20 After that, it is obtained by pyrolysis in the presence of oxygen.

(Formation of First Layer of Cathode by Pyrolysis)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved the metal salt of various combinations to the electrode base material for electrolysis, and thermally decomposing (baking) in presence of oxygen. The content rate of the metal in a 1st coating liquid is substantially the same as the 1st layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of intermediate layer)

An intermediate | middle layer is formed as needed, for example, is obtained by apply | coating the solution (2nd coating liquid) containing a palladium compound or a platinum compound on a base material, and then thermally decomposing in presence of oxygen. Alternatively, the nickel oxide intermediate layer may be formed on the surface of the substrate only by heating the substrate without applying the solution.

(Formation of First Layer of Cathode by Ion Plating)

The first layer 20 may be formed by ion plating.

As an example, the method of fixing a base material in a chamber, and irradiating an electron beam to a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and ruthenium is deposited on the substrate as ruthenium oxide.

(Formation of First Layer of Cathode by Plating)

The first layer 20 can also be formed by a plating method.

As an example, when a base material is used as a cathode and electrolytic plating is performed in the electrolyte solution containing nickel and tin, alloy plating of nickel and tin can be formed.

(Formation of First Layer of Cathode by Thermal Spray)

The first layer 20 can also be formed by thermal spraying.

As an example, by spraying nickel oxide particles on a substrate, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed.

The electrode for electrolysis in this embodiment can be used integrally with diaphragm, such as an ion exchange membrane and a microporous membrane. Therefore, the laminated body in this embodiment can be used as a membrane integrated electrode, and the replacement work of the cathode and the anode at the time of updating an electrode becomes unnecessary, and work efficiency improves significantly.

Moreover, according to the integral electrode with the diaphragm, such as an ion exchange membrane and a microporous membrane, electrolytic performance can be made to be equivalent to the performance at the time of new, or it can improve.

Hereinafter, the ion exchange membrane will be described in detail.

[Ion exchange membrane]

The ion exchange membrane is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various ion exchange membranes can be applied. In this embodiment, it is preferable to use the membrane main body containing the hydrocarbon type polymer or fluorine-containing polymer which has an ion exchange group, and the ion exchange membrane which has a coating layer formed on at least one surface of this membrane main body. In addition, it is preferable that the coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is 0.1-10 m 2 / g. The ion-exchange membrane of such a structure has little influence on the electrolytic performance by the gas which generate | occur | produces during electrolysis, and it tends to exhibit stable electrolytic performance.

The membrane of the perfluorocarbon polymer into which the ion exchange group is introduced is a sulfonic acid layer having an ion exchange group derived from a sulfo group (group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and an ion exchange group derived from a carboxyl group. It is provided with either a carboxylic sancheung having a - (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). In view of strength and dimensional stability, it is preferable to further have a reinforcing core material.

The inorganic particles and the binder will be described in detail in the description section of the coating layer below.

69 is a schematic sectional view showing one embodiment of the ion exchange membrane. The ion exchange membrane 1 has a membrane main body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group, and coating layers 11a and 11b formed on both surfaces of the membrane main body 10.

In the ion exchange membrane 1, the membrane main body 10 is a sulfonic acid layer 3 having an ion exchange group derived from a sulfo group (a group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and ions derived from a carboxyl group. exchanger has a strength and dimensional stability are enhanced by the carboxylic sancheung 2 provided, and the reinforcement core (4) having a (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). Since the ion exchange membrane 1 is provided with the sulfonic acid layer 3 and the carboxylic acid layer 2, it is suitably used as a cation exchange membrane.

In addition, the ion exchange membrane may have only one of a sulfonic acid layer and a carboxylic acid layer. In addition, the ion exchange membrane does not necessarily need to be reinforced by the reinforcing core, and the arrangement state of the reinforcing core is not limited to the example of FIG. 69.

(The membrane body)

First, the membrane main body 10 constituting the ion exchange membrane 1 will be described.

The membrane main body 10 may have a function of selectively permeating cations, and may include a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group. The structure and the material thereof are not particularly limited, and a suitable one can be appropriately selected. have.

The hydrocarbon-based polymer or fluorine-containing polymer having an ion exchange group in the membrane main body 10 can be obtained from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange precursor which can be an ion-exchange group, for example, by hydrolysis or the like. Specifically, for example, the main chain is made of a fluorinated hydrocarbon, and has a group (ion exchanger precursor) which can be converted into an ion exchanger by hydrolysis or the like as a pendant side chain, and also a polymer which can be melt processed (hereinafter referred to as "fluorine-containing polymer). (a) ") to produce the precursor of the membrane main body 10, and then convert the ion exchanger precursor into the ion exchanger to obtain the membrane main body 10.

The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the third group below. have. Moreover, it can also manufacture by the homopolymerization of 1 type of monomers chosen from any of the following 1st group, the following 2nd group, and the following 3rd group.

As a monomer of a 1st group, a vinyl fluoride compound is mentioned, for example. Examples of the vinyl fluoride compound include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and the like. In particular, when the ion exchange membrane is used as the alkali electrolytic membrane, the vinyl fluoride compound is preferably a perfluoro monomer, and is perfluoro selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Monomer is preferred.

As a monomer of a 2nd group, the vinyl compound which has a functional group which can be converted into a carboxylic acid type ion exchange group (carboxylic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted to a carboxylic acid group, for example, and the like can be _{CF 2 = CF (OCF 2 CYF} ) s -O (CZF) t monomers represented by -COOR (wherein, s is 0 An integer of -2, t represents an integer of 1 to 12, Y and Z each independently represents F or CF ₃ , and R represents a lower alkyl group, for example, a lower alkyl group is an alkyl group having 1 to 3 carbon atoms. .).

Among these, CF is _{2 = CF (OCF 2 CYF)} n -O (CF 2) _m -COOR compound represented by are preferred. Here n represents an integer of 0 to 2, m represents an integer of 1 to 4, Y represents F or CF ₃ , and R represents CH ₃ , C ₂ H ₅ or C ₃ H ₇ .

When the ion exchange membrane is used as a cation exchange membrane for alkali electrolysis, it is preferable to use at least a perfluoro compound as the monomer. However, since the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis, the alkyl group ( R) may not be a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

As a monomer of a 2nd group, the monomer shown below is more preferable among the above.

CF ₂ = CFOCF ₂ -CF (CF ₃ ) OCF ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CF [OCF ₂ -CF (CF ₃ )] ₂ O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₃ COOCH ₃ .

As a monomer of a 3rd group, the vinyl compound which has a functional group which can be converted into a sulfone type ion exchange group (sulfonic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted into a sulfonic acid is, for example, CF ₂ = a monomer represented by the _{CFO-X-CF 2 -SO 2} F are preferred (wherein, X represents an alkylene group of a perfluoroalkyl.). As these specific examples, the monomer etc. which are shown below are mentioned.

CF ₂ = CFOCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CF (CF ₂ ) ₂ SO ₂ F,

CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₂ OCF ₃ ) OCF ₂ CF ₂ SO ₂ F.

Among these, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F are more preferable.

The copolymer obtained from these monomers can be manufactured by the polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, especially the general polymerization method used with respect to tetrafluoroethylene. For example, in the non-aqueous method, inert solvents such as perfluorohydrocarbon and chlorofluorocarbon are used, and in the presence of radical polymerization initiators such as perfluorocarbon peroxide and azo compound, the temperature is 0 to 200 캜 and the pressure is 0.1 to 0.1. The polymerization reaction can be carried out under the condition of 20 MPa.

In the said copolymerization, the kind and ratio of the combination of the said monomers are not specifically limited, It selects according to the kind and quantity of the functional group to provide to the fluorine-containing polymer obtained. For example, in the case of using a fluorine-containing polymer containing only a carboxylic acid group, at least one monomer may be selected and copolymerized from the first group and the second group, respectively. In the case of using a fluorine-containing polymer containing only a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group and the third group, respectively. In the case of using a fluorine-containing polymer having a carboxylic acid group and a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group, the second group, and the third group, respectively. In this case, the target fluorine-containing polymer can also be obtained by separately polymerizing the copolymer composed of the first group and the second group and the copolymer composed of the first group and the third group, and then mixing the copolymer separately. . Moreover, although the mixing ratio of each monomer is not specifically limited, When increasing the quantity of functional groups per unit polymer, what is necessary is just to increase the ratio of the monomer chosen from the said 2nd group and the 3rd group.

Although the total ion exchange capacity of a fluorine-containing copolymer is not specifically limited, It is preferable that it is 0.5-2.0 mg equivalent / g, and it is more preferable that it is 0.6-1.5 mg equivalent / g. Here, total ion exchange capacity means the equivalent of the exchanger per unit weight of dry resin, and can be measured by neutralization titration etc.

In the membrane main body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorine-containing polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorine-containing polymer having a carboxylic acid group are laminated. . By using this layer structure as the membrane main body 10, the selective permeability of cations such as sodium ions can be further improved.

In the case where the ion exchange membrane 1 is disposed in the electrolytic cell, the sulfonic acid layer 3 is usually disposed on the anode side of the electrolytic cell and the carboxylic acid layer 2 on the cathode side of the electrolytic cell.

It is preferable that the sulfonic acid layer 3 is comprised from the material with low electrical resistance, and it is preferable that a film thickness is thicker than the carboxylic acid layer 2 from a viewpoint of film strength. The film thickness of the sulfonic acid layer 3 becomes like this. Preferably it is 2-25 times of the carboxylic acid layer 2, More preferably, it is 3-15 times.

It is preferable that the carboxylic acid layer 2 has high anion exclusion property even if it is thin. Anion-exclusion here means the property which wants to interrupt the invasion and permeation | transmission of anion to the ion exchange membrane 1. In order to improve anion exclusion, disposing a carboxylic acid layer having a small ion exchange capacity with respect to the sulfonic acid layer is effective.

As the fluorine-containing polymer used for the sulfonic acid layer 3, for example, a polymer obtained by using CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F as the third group of monomers is suitable.

Carboxylic acids referred to as the fluorine-based polymer for use in sancheung (2) is, for example, as monomers of group 2 _{CF 2 = CFOCF 2 CF (CF} 2) O (CF 2) a polymer obtained by using ₂ COOCH ₃ are suitable.

(Coating layer)

It is preferable that an ion exchange membrane has a coating layer on at least one surface of a membrane main body. 69, in the ion exchange membrane 1, the coating layers 11a and 11b are formed on both surfaces of the membrane main body 10, respectively.

The coating layer includes inorganic particles and a binder.

As for the average particle diameter of an inorganic particle, it is more preferable that it is 0.90 micrometer or more. If the average particle diameter of the inorganic particles is 0.90 µm or more, the durability against impurities as well as gas adhesion is greatly improved. In other words, a particularly significant effect is obtained by increasing the average particle diameter of the inorganic particles and by satisfying the above-described specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by crushing gemstones can be used. Preferably, the inorganic particles obtained by gemstone grinding can be suitably used.

In addition, the average particle diameter of an inorganic particle can be 2 micrometers or less. If the average particle diameter of an inorganic particle is 2 micrometers or less, it can prevent that a film | membrane is damaged by an inorganic particle. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 µm.

Here, an average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation).

It is preferable that the shape of an inorganic particle is an irregular shape. Resistance to impurities is further improved. In addition, the particle size distribution of the inorganic particles is preferably wide.

It is preferable that an inorganic particle contains at least 1 sort (s) of inorganic substance chosen from the group which consists of an oxide of a group IV element of a periodic table, a nitride of a group IV element of a periodic table, and a carbide of a group IV element of a periodic table. More preferably, they are particles of zirconium oxide from the viewpoint of durability.

It is preferable that this inorganic particle is an inorganic particle manufactured by crushing the gemstone of an inorganic particle, or it is preferable to make spherical particle | grains of the uniform diameter of particle | grains into an inorganic particle by melting and refine | purifying the gemstone of an inorganic particle.

Examples of the raw material grinding method include, but are not particularly limited to, ball mills, bead mills, colloid mills, conical mills, disc mills, edge mills, milling mills, hammer mills, pellet mills, VSI mills, willy mills, roller mills, and jet mills. Etc. can be mentioned. Moreover, it is preferable to wash | clean after grinding | pulverization, and it is preferable to be acid-processed at that time. As a result, impurities such as iron adhering to the surface of the inorganic particles can be reduced.

The coating layer preferably comprises a binder. A binder is a component which keeps inorganic particle on the surface of an ion exchange membrane, and comprises a coating layer. It is preferable that a binder contains a fluorine-containing polymer from a viewpoint of resistance to electrolyte solution or the product by electrolysis.

As a binder, it is more preferable that it is a fluorine-containing polymer which has a carboxylic acid group or a sulfonic acid group from a tolerance with respect to the electrolyte solution and the product by electrolysis, and adhesiveness to the surface of an ion exchange membrane. When forming a coating layer on the layer (sulfonic acid layer) containing a fluorine-containing polymer which has a sulfonic acid group, it is more preferable to use the fluorine-containing polymer which has a sulfonic acid group as a binder of this coating layer. Moreover, when forming a coating layer on the layer (carboxylic acid layer) containing the fluorine-containing polymer which has a carboxylic acid group, it is more preferable to use the fluorine-containing polymer which has a carboxylic acid group as a binder of this coating layer.

It is preferable that it is 40-90 mass%, and, as for content of an inorganic particle in a coating layer, it is more preferable that it is 50-90 mass%. Moreover, it is preferable that it is 10-60 mass%, and, as for content of a binder, it is more preferable that it is 10-50 mass%.

The distribution density of the coating layer in the ion exchange membrane is preferably 0.05 to 2 mg per cm 2. In addition, when an ion exchange membrane has a concave-convex shape on the surface, it is preferable that the distribution density of a coating layer is 0.5-2 mg per cm <2>.

It does not specifically limit as a method of forming a coating layer, A well-known method can be used. For example, the method of apply | coating the coating liquid which disperse | distributed inorganic particle to the solution containing a binder by spray etc. is mentioned.

(Reinforced heartwood)

It is preferable that the ion exchange membrane has a reinforcing core material disposed inside the membrane body.

The reinforcing core is a member for enhancing the strength and dimensional stability of the ion exchange membrane. By arrange | positioning a reinforcing core material inside a membrane main body, especially expansion and contraction of an ion exchange membrane can be controlled to a desired range. Such an ion exchange membrane can maintain excellent dimensional stability for a long time without being stretched more than necessary in electrolysis or the like.

The configuration of the reinforcing core is not particularly limited, and may be formed by spinning a yarn called reinforcing yarn, for example. The reinforcement yarn mentioned here is a member which constitutes a reinforcing core material, which can impart desired dimensional stability and mechanical strength to the ion exchange membrane, and refers to a yarn that can stably exist in the ion exchange membrane. By using the reinforcing core material which radiated such reinforcement yarn, further excellent dimensional stability and mechanical strength can be provided to the ion exchange membrane.

The material of the reinforcing core material and the reinforcing yarn used for this is not particularly limited, but it is preferable that the material is resistant to acids, alkalis, or the like. desirable.

Examples of the fluorine-containing polymer used in the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether polymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetra Fluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, vinylidene fluoride polymer (PVDF), and the like. Among these, it is preferable to use the fiber which consists of polytetrafluoroethylene from a heat resistant and chemical resistant viewpoint especially.

The diameter of the reinforcing sand used for the reinforcing core is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The weave density (number of insertion lines per unit length) is preferably 5 to 50 lines / inch. The form of the reinforcing core is not particularly limited, and for example, a woven fabric, a nonwoven fabric, a knitted fabric, or the like is used, but it is preferably a form of a woven fabric. In addition, the thickness of the woven fabric is preferably 30 to 250 m, more preferably 30 to 150 m.

As the woven fabric or knitted fabric, monofilament, multifilament or yarns, slit yarns, and the like thereof can be used, and the weaving method can use various weaving methods such as plain weave, leno weave, knitting, cord weave, and seerker.

The weaving method and arrangement of the reinforcing core material in the membrane main body are not particularly limited and can be appropriately arranged in consideration of the size and shape of the ion exchange membrane, the desired physical properties and the use environment for the ion exchange membrane, and the like.

For example, the reinforcing core may be disposed along a predetermined direction of the membrane body, but from the viewpoint of dimensional stability, the reinforcing core is disposed along the predetermined first direction, and a second direction substantially perpendicular to the first direction is provided. Therefore, it is preferable to arrange a separate reinforcing core material. By arranging the plurality of reinforcing cores so as to run substantially straight inside the longitudinal membrane body of the membrane body, further superior dimensional stability and mechanical strength can be imparted in multiple directions. For example, an arrangement for weaving the reinforcing core material (warp) disposed along the longitudinal direction and the reinforcing core material (weft) arranged along the transverse direction on the surface of the membrane body is preferable. Lion weaved by inserting the same number of wefts into the weaving plain weave by twisting and inserting warp and weft alternately, or by weaving two warp and leno weaving by twisting two warp and two or several lines. It is more preferable to use a woven fabric (a loom) from the viewpoint of dimensional stability, mechanical strength, and ease of manufacture.

In particular, it is preferable that the reinforcing core is disposed along both directions of the MD direction (Machine Direction direction) and the TD direction (Transverse Direction direction) of the ion exchange membrane. That is, it is preferable to be woven in the MD direction and the TD direction. Here, MD direction means the direction (flow direction) in which a membrane main body and various core materials (for example, a reinforced core material, a reinforcement yarn, a sacrificial yarn etc. mentioned later) are conveyed in the manufacturing process of the ion exchange membrane mentioned later, and a TD direction is It refers to a direction approximately perpendicular to the MD direction. The yarn woven along the MD direction is called MD yarn, and the yarn woven along the TD direction is called TD yarn. Usually, the ion exchange membrane used for electrolysis is rectangular, and a longitudinal direction becomes MD direction, and the width direction becomes a TD direction in many cases. By weaving the reinforced MD core material and the reinforced TD core material, it is possible to give even more excellent dimensional stability and mechanical strength in multiple directions.

The spacing of the reinforcing cores is not particularly limited and can be appropriately arranged in consideration of desired physical properties, use environment, and the like for the ion exchange membrane.

The opening ratio of the reinforcing core material is not particularly limited, and is preferably 30% or more, more preferably 50% or more and 90% or less. The opening ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane.

The opening ratio of the reinforcing core is the total area (B) of the surface through which substances such as ions (electrolyte and cation (for example, sodium ions) contained) in the area (A) of either surface of the membrane body can pass. The ratio of (B / A). The total area (B) of the surface through which substances such as ions can pass can be referred to as the total area of the region where cations, electrolytes, and the like are not blocked by the reinforcing core included in the ion exchange membrane.

70 is a schematic view for explaining the aperture ratio of the reinforcing core material constituting the ion exchange membrane. FIG. 70 enlarges a part of the ion exchange membrane and shows only the arrangement of the reinforcing core materials 21 and 22 in the region, and the illustration of the other members is omitted.

The total area C of the reinforcement core from the area A of the region including the area of the reinforcement core, which is also surrounded by the reinforcement core 21 arranged in the longitudinal direction and the reinforcement core 22 arranged in the horizontal direction. By subtracting, the total area B of the area through which substances such as ions in the area A of the area can pass can be obtained. That is, an opening ratio can be calculated | required by following formula (I).

Aperture ratio = (B) / (A) = ((A)-(C)) / (A). (I)

Among the reinforcing cores, a particularly preferable form is a tape yarn or a highly oriented monofilament containing PTFE in view of chemical resistance and heat resistance. Specifically, a high-strength porous sheet made of PTFE is a tape yarn slitted in tape form, or a 50 to 300 denier of a highly oriented monofilament made of PTFE, and a woven density of 10 to 50 lines / inch. It is more preferable that it is a reinforcement core material whose thickness is the range of 50-100 micrometers. It is more preferable that the opening ratio of the ion exchange membrane including such a reinforcing core material is 60% or more.

Examples of the shape of the reinforcing yarn include round yarns and tape-like yarns.

(Communication hole)

It is preferable that the ion exchange membrane has a communication hole inside the membrane main body.

The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, a communication hole is a tubular hole formed in the inside of a membrane main body, and is formed by eluting the sacrificial core material (or sacrificial thread) mentioned later. The shape and diameter of the communication hole can be controlled by selecting the shape and diameter of the sacrificial core material (sacrificial yarn).

By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured at the time of electrolysis. Although the shape of a communication hole is not specifically limited, According to the manufacturing method mentioned later, it can be set as the shape of the sacrificial core material used for formation of a communication hole.

The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With such a structure, in the part where the communication hole is formed in the cathode side of the reinforcing core material, ions (for example, sodium ions) transported through the electrolyte solution filled in the communication hole can also flow to the cathode side of the reinforcing core material. As a result, since the flow of cation is not blocked, the electrical resistance of the ion exchange membrane can be made lower.

The communication hole may be formed along only one predetermined direction of the membrane main body constituting the ion exchange membrane, but is formed in both the longitudinal direction and the transverse direction of the membrane main body in view of exhibiting more stable electrolytic performance. desirable.

[Production method]

As a suitable manufacturing method of an ion exchange membrane, the method of having the following (1) process-(6) process is mentioned.

(1) Process: The process of manufacturing the fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(2) Process: If necessary, a sacrificial yarn is disposed between adjacent reinforcing cores by at least weaving a plurality of reinforcing cores and a property of dissolving in an acid or alkali and forming at least a communication hole. To obtain the finished reinforcement.

(3) Process: The process of film-forming the said fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(4) Step: The step of embedding the reinforcing material in the film as necessary to obtain a membrane body having the reinforcing material disposed therein.

(5) Process: The process (hydrolysis process) of hydrolyzing the membrane main body obtained at process (4).

(6) Process: The process (coating process) of forming a coating layer in the film main body obtained at the process (5).

Hereinafter, each process is explained in full detail.

(1) Process: process for producing fluorine-containing polymer

In the step (1), the fluorine-containing polymer is produced by using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of a fluorine-containing polymer, in the manufacture of the fluorine-containing polymer which forms each layer, the mixing ratio of the monomer of a raw material may be adjusted.

(2) Process: manufacturing process of reinforcement

A reinforcing material is a woven fabric etc. which woven the reinforcement yarn. The reinforcing material is embedded in the film to form the reinforcing core material. When using an ion exchange membrane having communication holes, the sacrificial yarn is also woven into the reinforcing material. In this case, the blending amount of the sacrificial material is preferably 10 to 80 mass%, more preferably 30 to 70 mass% of the entire reinforcing material. By weaving a sacrificial thread, the mesh shift | offset of a reinforcement core material can also be prevented.

The sacrificial material has solubility in a film production process or an electrolytic environment, and rayon, polyethylene terephthalate (PET), cellulose, polyamide, and the like are used. Moreover, polyvinyl alcohol etc. which have a thickness of 20-50 denier and consist of monofilament or multifilament are also preferable.

In the step (2), by adjusting the arrangement of the reinforcing core material or the sacrificial material, the opening ratio, the arrangement of the communication holes, and the like can be controlled.

(3) process: filming process

In the step (3), the fluorine-containing polymer obtained in the step (1) is filmed using an extruder. A single layer structure may be sufficient as a film, and as above-mentioned, the two-layered structure of a sulfonic acid layer and a carboxylic acid layer may be sufficient, and the multilayered structure of three or more layers may be sufficient as it.

As a method of film-forming, the following are mentioned, for example.

A method of filming each of the fluorine-containing polymer having a carboxylic acid group and the fluorine-containing polymer having a sulfonic acid group separately.

A method in which a fluorine-containing polymer having a carboxylic acid group and a fluorine-containing polymer having a sulfonic acid group are co-extruded into a composite film.

In addition, a plurality of films may be sufficient respectively. Moreover, coextrusion of different kinds of films is preferable because it contributes to raising the adhesive strength of an interface.

(4) step: the step of obtaining the membrane body

In the step (4), the film body in which the reinforcing material is embedded is obtained by embedding the reinforcing material obtained in the step (2) inside the film obtained in the step (3).

As a preferable formation method of a film main body, (i) the fluorine-containing polymer which has a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) located in the cathode side (henceforth, the layer which consists of this is called a 1st layer), And forming a fluorine-containing polymer having a sulfonic acid group precursor (e.g., a sulfonylfluoride functional group) (hereinafter, referred to as a second layer) by a coextrusion method, and heating and vacuum source as necessary. Is laminated on a flat plate or drum having a large number of pores on the surface of the reinforcing material and the second layer / first layer composite film in the order of a reinforcing material and a heat-resistant release paper having air permeability. Integrating while removing air between each layer by decompression under temperature; (ii) Apart from the second layer / first layer composite film, the fluorine-containing polymer (third layer) having a sulfonic acid group precursor is previously filmed alone, and the surface is heated and heated using a vacuum source if necessary. The laminated film was laminated in the order of a composite film consisting of a third layer film, a reinforcing core material, and a second layer / first layer via a heat-resistant release paper having air permeability on a flat plate or a drum having a large number of pores thereon. The method of integrating, removing the air between each layer by pressure reduction under the temperature which melt | dissolves is mentioned.

Here, coextrusion of a 1st layer and a 2nd layer contributes to raising the adhesive strength of an interface.

Moreover, the method of integrating under reduced pressure has the feature that the thickness of the 3rd layer on a reinforcement material becomes large compared with the pressure press method. In addition, since the reinforcing material is fixed to the inner surface of the membrane main body, it has the performance of sufficiently maintaining the mechanical strength of the ion exchange membrane.

In addition, the variation of lamination described here is an example, and considering the desired layer structure, physical properties, etc. of a film body, a suitable lamination pattern (for example, the combination of each layer, etc.) can be selected, and then co-extruded.

Further, in order to further improve the electrical performance of the ion exchange membrane, a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is further interposed between the first layer and the second layer. It is also possible to use a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor instead of the layer.

The method for forming the fourth layer may be a method of separately preparing a fluorine-containing polymer having a carboxylic acid group precursor and a fluorine-containing polymer having a sulfonic acid group precursor, and then mixing the monomers with the carboxylic acid group precursor and the sulfonic acid group precursor. The method of copolymerizing the monomer which has the thing may be used.

In the case where the fourth layer is configured as an ion exchange membrane, the coextruded film of the first layer and the fourth layer is molded, and the third layer and the second layer are filmed independently of this, by the method described above. You may laminate | stack and three layers of a 1st layer / 4th layer / 2nd layer may be film-formed by coextrusion at once.

In this case, the direction in which the extruded film flows is the MD direction. In this way, a membrane body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material.

In addition, the ion exchange membrane preferably has a protruding portion, that is, a convex portion, made of a fluorine-containing polymer having a sulfonic acid group, on the surface side of the sulfonic acid layer. It does not specifically limit as a method of forming such a convex part, The well-known method of forming a convex part in the resin surface can be employ | adopted. Specifically, the method of embossing on the surface of a film main body is mentioned, for example. For example, when the said composite film, reinforcing material, etc. are integrated, the said convex part can be formed by using the release paper previously embossed. When forming a convex part by embossing, control of the height and placement density of a convex part can be performed by controlling the emboss shape (shape of a release paper) to be transferred.

(5) hydrolysis process

In the step (5), the membrane body obtained in the step (4) is hydrolyzed to convert the ion exchanger precursor into the ion exchanger (hydrolysis step).

In the step (5), the elution hole can be formed in the membrane main body by dissolving and removing the sacrificial yarn contained in the membrane main body with an acid or an alkali. In addition, the sacrificial yarn may remain in the communication hole without being completely dissolved and removed. In addition, the sacrificial yarn remaining in the communication hole may be dissolved and removed by the electrolytic solution when the ion exchange membrane is provided for electrolysis.

The sacrificial yarn is soluble in acid or alkali in the ion exchange membrane production process or in an electrolytic environment, and communication holes are formed in the site by dissolving the sacrificial material.

The step (5) can be performed by immersing the membrane body obtained in the step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (dimethyl sulfoxide) can be used.

It is preferable that the said mixed solution contains 2.5-4.0 N of KOH, and contains 25-35 mass% of DMSO.

As temperature of hydrolysis, it is preferable that it is 70-100 degreeC. The higher the temperature, the thicker the apparent thickness. More preferably, it is 75-100 degreeC.

It is preferable that it is 10 to 120 minutes as time of hydrolysis. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes.

Here, the process of forming a communication hole by eluting a sacrificial yarn is demonstrated in detail. 71 (a) and 71 (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane.

In FIGS. 71A and 71B, only the communication holes 504 formed by the reinforcing yarn 52, the sacrificial yarn 504a, and the sacrificial yarn 504a are shown. The illustration is omitted.

First, the reinforcement yarn 52 which comprises a reinforcing core material in an ion exchange membrane, and the sacrificial yarn 504a for forming the communication hole 504 in an ion exchange membrane are used as a knitted reinforcement material. And the communication hole 504 is formed by eluting the sacrificial yarn 504a in the process (5).

According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a may be adjusted in accordance with the arrangement of the reinforcing core and the communication hole in the membrane main body of the ion exchange membrane.

In FIG. 71 (a), although the reinforcement of the plain weave which woven the reinforcement yarn 52 and the sacrificial yarn 504a in both the longitudinal direction and the horizontal direction in the ground is illustrated, the reinforcement yarn in a reinforcement material as needed. The arrangement of the 52 and the victim 504a can be changed.

(6) coating process

In the step (6), the coating layer can be formed by preparing a coating liquid containing the inorganic particles obtained by gemstone grinding or melting of the gemstone and a binder, and applying and drying the coating liquid on the surface of the ion exchange membrane obtained in the step (5). .

As a binder, after hydrolyzing the fluorine-containing polymer having an ion exchange group precursor with an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH), it is immersed in hydrochloric acid to replace the counter ion of the ion exchange group with H ⁺ . One binder (eg, a fluorine-containing polymer having a carboxyl or sulfo group) is preferred. Since it becomes easy to melt | dissolve in water and ethanol mentioned later by this, it is preferable.

This binder is dissolved in a solution in which water and ethanol are mixed. Moreover, the preferable volume ratio of water and ethanol is 10: 1-1:10, More preferably, it is 5: 1-1: 5, More preferably, it is 2: 1-1: 2. In the solution thus obtained, the inorganic particles are dispersed by a ball mill to obtain a coating solution. At this time, the average particle diameter of a particle | grains, etc. can also be adjusted by adjusting the time and the rotation speed at the time of dispersion. In addition, the preferable compounding quantity of an inorganic particle and a binder is as above-mentioned.

The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, but is preferably a light coating liquid. Thereby, it becomes possible to apply | coat uniformly to the surface of an ion exchange membrane.

In addition, when dispersing the inorganic particles, a surfactant may be added to the dispersion. As surfactant, a nonionic surfactant is preferable, For example, HS-210, NS-210, P-210, E-212 by Nichi-yu Corporation, etc. are mentioned.

An ion exchange membrane is obtained by apply | coating the obtained coating liquid to the surface of an ion exchange membrane by spray coating or roll coating.

[Microporous membrane]

As described above, the microporous membrane of the present embodiment is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various microporous membranes can be applied.

Although the porosity of the microporous membrane of this embodiment is not specifically limited, For example, it can be 20-90, Preferably it is 30-85. The porosity can be calculated by the following formula, for example.

Porosity = (1- (Dry Film Weight in Dry State) / (Volume calculated from the thickness, width and length of the film and weight calculated from the density of the film material)) × 100

Although the average pore diameter of the microporous membrane of this embodiment is not specifically limited, For example, it can be 0.01 micrometer-10 micrometers, Preferably it is 0.05 micrometer-5 micrometers. The average pore diameter is, for example, the film is vertically cut in the thickness direction, and the cut surface is observed by FE-SEM. It can obtain | require by measuring and averaging about 100 points of the diameter of the hole observed.

Although the thickness of the microporous film of this embodiment is not specifically limited, For example, it can be 10 micrometers-1000 micrometers, Preferably it is 50 micrometers-600 micrometers. The said thickness can be measured using a micrometer (made by Mitsutoyo Corporation) etc., for example.

Specific examples of the microporous membranes described above include Agir's Zirfon Perl UTP 500 (also referred to as Zirfon membrane in this embodiment), International Publication No. 2013-183584, International Publication No. 2016-203701, etc. The things described are mentioned.

In this embodiment, it is preferable that a diaphragm contains the 1st ion exchange resin layer and the 2nd ion exchange resin layer which has EW (ion exchange equivalent) different from this 1st ion exchange resin layer. Moreover, it is preferable that a diaphragm contains the 1st ion exchange resin layer and the 2nd ion exchange resin layer which has a functional group different from this 1st ion exchange resin layer. An ion exchange equivalent can be adjusted with the functional group to introduce | transduce, and the functional group which can be introduce | transduced is as above-mentioned.

In this embodiment, it is preferable that the part of the laminated body 25 clamped between the positive electrode gasket 12 and the negative electrode gasket 13 is a non-conductive surface. In addition, a "conduction surface" corresponds to the part designed so that electrolyte may be moved between the anode chamber and the cathode chamber, and "non-conduction surface" is a portion which does not correspond to the conduction surface.

In addition, in this embodiment, although the outermost periphery of a laminated body may be located in the energization surface direction inner side rather than outermost periphery of an anode side gasket and a cathode side gasket, it may be located outside, but it is preferable to be located outside. When comprised in this way, since the outermost periphery located in the outer side can be caught, workability at the time of assembling an electrolytic cell tends to improve. Here, the outermost edge of the laminate is the outermost edge in a state where the diaphragm and the electrode for electrolysis are combined. That is, if the outermost edge of the electrode for electrolysis is outside the contact surface outside the outermost edge of the diaphragm, it means the outermost edge of the electrode for electrolysis, and if there is the outermost edge of the electrode for electrolysis inside the contact surface inside each other than the outermost edge of the diaphragm It means the outermost part of the diaphragm.

This positional relationship will be described with reference to FIGS. 72 and 73. 72 and 73 show the positional relationship of a gasket and a laminated body especially when the two electrolytic cells shown, for example in FIG. 64B are observed from (alpha) direction. 72 and 73, the rectangular gasket A having an opening in the center is positioned at the forefront. Thereafter, the rectangular diaphragm B is located, and thereafter, the rectangular electrolytic electrode C is located. That is, the opening part of gasket A is a part corresponding to the energizing surface of a laminated body.

In FIG. 72, the outermost peripheral A1 of the gasket A is located in the conduction surface direction inner side than the outermost peripheral B1 of the diaphragm B and the outermost peripheral C1 of the electrolytic electrode C. In FIG.

In FIG. 73, the outermost peripheral A1 of the gasket A is located outside the conducting surface direction than the outermost peripheral C1 of the electrolytic electrode C, but the outermost peripheral B1 of the diaphragm B is located outside the outermost peripheral A1 of the gasket A. Is located.

In the present embodiment, the laminate may be sandwiched between the anode side gasket and the cathode side gasket, and the electrolytic electrode itself may not be directly sandwiched between the anode side gasket and the cathode side gasket. That is, as long as the electrolytic electrode itself is fixed to the diaphragm, only the diaphragm may be directly sandwiched by the anode side gasket and the cathode side gasket. In the present embodiment, from the viewpoint of more stably fixing the electrolytic electrode in the electrolytic cell, it is preferable that both of the electrolytic electrode and the diaphragm are sandwiched between the anode side gasket and the cathode side gasket.

In the present embodiment, the diaphragm and the electrode for electrolysis are fixed at least by the positive electrode gasket and the negative electrode gasket and exist as a laminate, but may have other fixing structures, for example, a fixing structure illustrated below can be adopted. . In addition, only 1 type may be employ | adopted for each fixing structure, and may be employ | adopted in combination of 2 or more type.

In this embodiment, it is preferable that at least one part of the electrode for electrolysis is fixed through the diaphragm. This aspect is demonstrated using FIG. 74A.

In FIG. 74A, at least a part of the electrolytic electrode 2 is fixed through the diaphragm 3. 74A shows an example in which the electrolytic electrode 2 is a metal porous electrode. That is, although the part of the electrode for electrolysis 2 is shown independently in FIG. 74A, these are connected and have shown the cross section of the integral metal porous electrode (it is the same also in FIGS. 75-78 below).

In such an electrode structure, for example, when the diaphragm 3 at a predetermined position (position to be fixed) is pressed against the electrolytic electrode 2, the diaphragm (within the uneven structure or the hole structure on the surface of the electrolytic electrode 2) A part of 3) enters, and the recessed part of the electrode surface and the convex part around a hole penetrate the diaphragm 3, Preferably it penetrates out to the outer surface 3b of the diaphragm 3 as shown to FIG. 74A.

As described above, the fixed structure of FIG. 74A can be manufactured by pressing the diaphragm 3 against the electrode 2 for electrolysis, but in this case, the thermocompression bonding and heat suction in the state which softened the diaphragm 3 by heating. do. As a result, the electrolytic electrode 2 penetrates through the diaphragm 3. Alternatively, the membrane 3 may be melted. In this case, it is preferable to suck the diaphragm 3 from the outer surface 2b side (back side) of the electrolytic electrode 2 in the state shown in FIG. 74B. Moreover, the area | region which pressed the diaphragm 3 to the electrolytic electrode 2 comprises "fixing part."

The fixed structure shown in FIG. 74A can be observed with a magnifying glass (loupe), an optical microscope, or an electron microscope. In addition, when the electrolytic electrode 2 penetrates through the diaphragm 3, by a conduction test using a tester or the like between the outer surface 3b of the diaphragm 3 and the outer surface 2b of the electrolytic electrode 2. , It is possible to guess the fixed structure of Fig. 74A.

In this embodiment, it is preferable that at least a part of the electrode for electrolysis is fixed in the inside of a diaphragm in a fixed part. This aspect is demonstrated using FIG. 75A.

As described above, the surface of the electrolytic electrode 2 has an uneven structure or a hole structure. In the embodiment shown in FIG. 75A, a part of the electrode surface penetrates into and is fixed to the diaphragm 3 at a predetermined position (position to be fixed). The fixed structure shown in FIG. 75A can be manufactured by pressing the diaphragm 3 to the electrode 2 for electrolysis. In this case, it is preferable to form the fixed structure of FIG. 75A by thermocompression bonding and heat suction in the state which softened the diaphragm 3 by heating. Alternatively, the diaphragm 3 may be melted to form the fixed structure of FIG. 75A. In this case, it is preferable to suck the diaphragm 3 from the outer surface 2b side (back side) of the electrode 2 for electrolysis.

The fixed structure shown in FIG. 75A can be observed with a magnifying glass (loupe), an optical microscope, or an electron microscope. In particular, after embedding the sample, a method of creating and observing a cross section by a microtome is preferable. In addition, in the fixed structure shown in FIG. 75A, since the electrolytic electrode 2 does not penetrate the diaphragm 3, the outer surface 3b of the diaphragm 3 and the outer surface 2b of the electrolytic electrode 2 are shown. The conduction by the conduction test between is not confirmed.

In this embodiment, it is preferable to further have a fixing member for fixing a diaphragm and an electrode for electrolysis in a laminated body. This aspect is demonstrated using FIGS. 76A-76C.

The fixing structure shown in FIG. 76A uses the fixing member 7 which is separate from the electrolytic electrode 2 and the diaphragm 3, and the fixing member 7 has the electrolytic electrode 2 and the diaphragm ( 3) It is a structure fixed through. The electrolytic electrode 2 does not necessarily need to penetrate through the fixing member 7, but may be fixed so as not to be separated from the diaphragm 3 by the fixing member 7. The material of the fastening member 7 is not specifically limited, As the fastening member 7, what consists of metal, resin, etc. can be used, for example. In the case of a metal, nickel, nichrome, titanium, stainless steel (SUS), etc. are mentioned. These oxides may be sufficient. Examples of the resin include fluororesins (e.g. PTFE (polytetrafluoroethylene), PFA (copolymer of tetrafluoroethylene and perfluoroalkoxy ethylene), ETFE (copolymer of tetrafluoroethylene and ethylene), The material of the diaphragm 3 described below, PVDF (polyvinylidene fluoride), EPDM (ethylene propylene diene rubber), PP (polyethylene), PE (polypropylene), nylon, aramid, etc. can be used.

In the present embodiment, for example, using a thread-shaped metal or resin, as shown in Figs. 76B and C, predetermined positions (fixed) between the electrode 2 for electrolysis and the outer surfaces 2b and 3b of the diaphragm 3 are fixed. It may also be fixed by sewing). It is also possible to fix the electrolytic electrode 2 and the diaphragm 3 using a fixing mechanism such as a tacker.

The fixed structure shown in FIG. 77 is a structure in which an organic resin (adhesive layer) is interposed and fixed between the electrolytic electrode 2 and the diaphragm 3. That is, in FIG. 77, the organic resin as the fixing member 7 is arranged at a predetermined position (position to be fixed) between the electrolytic electrode 2 and the diaphragm 3 and fixed by adhesion. For example, both or one of the inner surface 2a of the electrolytic electrode 2 or the inner surface 3a of the diaphragm 3 or the inner surfaces 2a and 3a of the electrolytic electrode 2 and the diaphragm 3. Organic resin is apply | coated to it. And the fixed structure shown in FIG. 77 can be formed by joining the electrolytic electrode 2 and the diaphragm 3. Although the material of an organic resin is not specifically limited, For example, fluororesin (for example, PTFE, PFE, PFPE), resin similar to the material which comprises the above-mentioned diaphragm 3, etc. can be used. In addition, a commercially available fluorine adhesive, a PTFE dispersion, or the like can also be used as appropriate. In addition, general purpose vinyl acetate adhesives, ethylene vinyl acetate copolymer adhesives, acrylic resin adhesives, α-olefin adhesives, styrene-butadiene rubber latex adhesives, vinyl chloride resin adhesives, chloroprene adhesives, nitrile rubber adhesives, urethane rubber adhesives, and epoxy resins Adhesives, silicone resin adhesives, modified silicone adhesives, epoxy-modified silicone resin adhesives, silylated urethane resin adhesives, cyanoacrylate adhesives, and the like.

In this embodiment, you may use the organic resin which melt | dissolves in electrolyte solution, or dissolves and decomposes during electrolysis. The organic resin dissolved in the electrolyte or dissolved and decomposed during electrolysis is not limited to the following, but is not limited to, for example, vinyl acetate adhesive, ethylene vinyl acetate copolymer adhesive, acrylic resin adhesive, α-olefin adhesive, and styrene butadiene rubber latex. Adhesive, vinyl chloride resin adhesive, chloroprene adhesive, nitrile rubber adhesive, urethane rubber adhesive, epoxy adhesive, silicone resin adhesive, modified silicone adhesive, epoxy / modified silicone resin adhesive, silylated urethane resin adhesive, cyanoacrylate adhesive Etc. can be mentioned.

The fixed structure shown in FIG. 77 can be observed with an optical microscope or an electron microscope. In particular, after embedding the sample, a method of creating and observing a cross section by a microtome is preferable.

In this embodiment, it is preferable that at least one part of the fixing member grips the diaphragm and the electrode for electrolysis outside. This aspect is demonstrated using FIG. 78A.

The fixing structure shown in FIG. 78A is a structure in which the electrolytic electrode 2 and the diaphragm 3 are gripped from the outside and fixed. That is, between the outer surface 2b of the electrolytic electrode 2 and the outer surface 3b of the diaphragm 3 is clamped by the holding member as the fixing member 7, and is fixed. In the fixing structure shown to FIG. 78A, the state which the holding member dug in the electrolytic electrode 2 or the diaphragm 3 is also included. As a holding member, a tape, a clip, etc. are mentioned, for example.

In this embodiment, you may use the holding member melt | dissolved in electrolyte solution. As a holding member melt | dissolved in electrolyte solution, the tape made from PET, a clip, the tape made from PVA, a clip, etc. are mentioned, for example.

In the fixing structure shown in FIG. 78A, unlike the FIGS. 74-77, the interface of the electrolytic electrode 2 and the diaphragm 3 was not bonded, but each inner surface of the electrolytic electrode 2 and the diaphragm 3 is shown. (2a, 3a) are only in a contact or facing state, and by removing the holding member, the fixed state of the electrolytic electrode 2 and the diaphragm 3 can be released and separated.

Although not shown in FIG. 78A, the electrolytic electrode 2 and the diaphragm 3 may be fixed to the electrolytic cell by using a gripping member.

Moreover, in this embodiment, it is preferable that at least one part of the fixing member fixes the diaphragm and the electrode for electrolysis by magnetic force. This aspect is demonstrated using FIG. 78B.

The fixing structure shown in FIG. 78B is a structure in which the electrolytic electrode 2 and the diaphragm 3 are gripped and fixed from the outside. The difference from FIG. 78A is that a pair of magnets are used as the holding member as the fixing member. In the aspect of the fixing structure shown to FIG. 78B, after attaching the laminated body 1 to an electrolytic cell, the holding member may be left as it is at the time of an electrolytic cell operation, and may be removed from the laminated body 1.

Although not shown in FIG. 78B, the electrolytic electrode 2 and the diaphragm 3 may be fixed to the electrolytic cell by using a holding member. In addition, when a magnetic material that adheres to a magnet to a part of the material of the electrolytic cell is used, one gripping material is provided on the diaphragm surface side, and the electrolytic cell, the electrolytic electrode 2 and the diaphragm 3 are sandwiched therebetween. It can also be fixed.

In addition, a plurality of lines of fixing portions may be provided. That is, 1, 2, 3,... Toward the inner side from the contour side of the laminate 1. n fixing parts can be arranged. n is an integer of 1 or more. The m-th (m <n) fixing part and the L-th (m <L≤n) fixing part can be formed in different fixing patterns.

The fixed part formed in the electricity supply surface is preferably a line symmetrical shape. There exists a tendency which can suppress stress concentration by this. For example, when two orthogonal directions are made into the X direction and the Y direction, a fixed part can be comprised by arrange | positioning one by one in each of the X direction and the Y direction, or a plurality in equal intervals in each of the X direction and the Y direction. . The number of fixing portions in the X and Y directions is not limited, but is preferably 100 or less in the X and Y directions, respectively. In addition, from the viewpoint of securing the surface area of the energized surface, the number of fixing portions in the X direction and the Y direction is preferably 50 or less, respectively.

In the fixing part in this embodiment, when it has the fixing structure shown to FIG. 74A or 76, it is preferable to apply a sealing material on the film surface of a fixing part from a viewpoint of preventing the short circuit resulting from the contact of an anode and a cathode. Do. As a sealing material, the raw material demonstrated about the said adhesive agent can be used, for example.

As mentioned above, although the laminated body in this embodiment may have various fixing parts in various positions, it is preferable that these fixing parts exist in a non-conductive surface from a viewpoint of ensuring sufficient electrolytic performance.

As mentioned above, although the laminated body in this embodiment may have various fixing parts in various positions, in particular, in the part (non-fixed part) in which the fixing part does not exist, the "electromotive force" mentioned above by the electrolytic electrode is mentioned. It is desirable to satisfy. That is, it is preferable that the force applied per unit mass and unit area in the non-fixing part of the electrode for electrolysis is less than 1.5 N / mg · cm 2.

Moreover, in this embodiment, it is preferable that a diaphragm contains the ion exchange membrane containing an organic resin in a surface layer, and the electrode for electrolysis is fixed by the said organic resin. Such organic resin is as mentioned above, and can be formed as a surface layer of an ion exchange membrane by various well-known methods.

(Hydraulic)

In the electrolytic cell of this embodiment, the electrolytic cell in the case of performing electrolytic electrolysis has the structure which changed the ion exchange membrane in the electrolytic cell in the case of performing the above-mentioned salt electrolysis to a microporous membrane. In addition, since the raw material to be supplied is water, it differs from the electrolytic cell in the case of performing the above-mentioned salt electrolysis. As for other configurations, the same configuration as the electrolytic cell in the case of performing salt electrolysis can also be adopted. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. However, in the case of hydrolysis, since oxygen gas is only generated in the anode chamber, the same material as the cathode chamber is used. Can be used. For example, nickel etc. can be mentioned. In addition, the anode coating is suitably a catalyst coating for oxygen generation. Examples of catalyst coatings include metals, oxides, hydroxides, and the like of platinum group metals and transition metals. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used.

(Manufacturing method of electrolytic bath and update method of laminated body)

The updating method of the laminated body in the electrolytic cell of this embodiment is a process of taking out the said laminated body from an electrolytic cell by isolate | separating the laminated body in this embodiment from an anode side gasket and a cathode side gasket, an anode side gasket, It has a process of sandwiching a new laminated body between cathode side gaskets. In addition, a new laminated body means the laminated body in this embodiment, and at least one of an electrode for electrolysis and a diaphragm should just be a new article.

In the process of clamping the laminate, from the viewpoint of more stably fixing the electrolytic electrode in the electrolytic cell, it is preferable that both of the electrolytic electrode and the diaphragm are sandwiched between the anode side gasket and the cathode side gasket.

Moreover, the manufacturing method of the electrolytic cell of this embodiment has a process of clamping the laminated body in this embodiment between an anode side gasket and a cathode side gasket.

Since the manufacturing method of the electrolytic cell of this embodiment and the updating method of a laminated body are comprised as mentioned above, the working efficiency at the time of electrode update in an electrolytic cell can be improved, and the outstanding electrolytic performance can be obtained even after updating.

Also in the process of clamping the said laminated body, it is preferable that both the electrode for electrolysis and a diaphragm are pinched by the anode side gasket and the cathode side gasket from a viewpoint of fixing the electrolytic electrode more stably in an electrolytic cell.

Fifth Embodiment

Here, the fifth embodiment of the present invention will be described in detail with reference to FIGS. 91 to 102.

[Method of Manufacturing Electrolyzer]

A method for producing an electrolytic cell according to a fifth embodiment (hereinafter simply referred to as "the present embodiment" in the section of <Fifth Embodiment>) includes an anode, a cathode facing the anode, and between the anode and the cathode. A method for producing a new electrolytic cell by arranging an electrode for electrolysis or a laminate of the electrode for electrolysis and a new diaphragm in an existing electrolytic cell having a diaphragm disposed on the coil, wherein the winding of the electrolytic electrode or the laminate It is using the font. As mentioned above, according to the manufacturing method of the electrolytic cell which concerns on this embodiment, since the electrode for electrolysis or the winding body of the laminated body of this electrolytic electrode and a new diaphragm is used, the electrode for electrolysis or lamination | stacking when using as a member of an electrolytic cell The sieve can be sized down and then transported to improve the working efficiency at the time of electrode update in the electrolytic cell.

In the present embodiment, the existing electrolytic cell includes a positive electrode, a negative electrode facing the positive electrode, and a diaphragm disposed between the positive electrode and the negative electrode as a constituent member, in other words, an electrolytic cell. The existing electrolytic cell is not specifically limited as long as it contains the said structural member, Various well-known structures can be applied.

In the present embodiment, the new electrolytic cell further includes an electrode for electrolysis or a laminate in addition to a member that already functions as an anode or a cathode in the existing electrolytic cell. That is, the "electrode for electrolysis" arrange | positioned at the time of manufacture of a new electrolytic cell functions as an anode or a cathode, and is separate from the cathode and anode in an existing electrolytic cell. In the present embodiment, even when the electrolytic performance of the positive electrode and / or the negative electrode deteriorates due to the operation of the existing electrolytic cell, the performance of the positive electrode and / or the negative electrode can be updated by disposing the electrode for electrolysis separate from these. In addition, when using a laminated body in this embodiment, since a new ion exchange membrane is arrange | positioned together, the performance of the ion exchange membrane whose performance deteriorated with operation can also be updated simultaneously. The term "update performance" as used herein means that the performance is equal to the initial performance which the existing electrolytic cell had before being provided for operation, or the performance is higher than the initial performance.

In this embodiment, the existing electrolytic cell assumes "electrolyte already provided for operation", and the new electrolytic cell assumes "electrolyte not provided for operation yet". That is, once the electrolytic cell manufactured as a new electrolytic cell is provided to operation, it becomes "the existing electrolytic cell in this embodiment", and it is "the new electrolytic cell in this embodiment" which arrange | positioned the electrode or laminated body for this existing electrolytic cell. Becomes

EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of an electrolytic cell is explained in full detail, for example, when salt electrolysis is performed using an ion exchange membrane as a diaphragm. In addition, "electrolyzer in this embodiment" includes both "existing electrolyzer in this embodiment" and "new electrolyzer in this embodiment", unless specifically mentioned in the term of <5th embodiment>. will be.

[Electrolysis cell]

First, the electrolytic cell which can be used as a structural unit of the electrolytic cell in this embodiment is demonstrated.

91 is a cross-sectional view of the electrolytic cell 1.

The electrolytic cell 1 includes the anode chamber 10, the cathode chamber 20, the partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, and the anode provided in the anode chamber 10. 11 and a cathode 21 provided in the cathode chamber 20. If necessary, the base 18a and the reverse current absorbing layer 18b formed on the base 18a may be provided, and the reverse current absorber 18 provided in the cathode chamber may be provided. The positive electrode 11 and the negative electrode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 has the following cathode structure. The negative electrode structure 40 includes a negative electrode chamber 20, a negative electrode 21 provided in the negative electrode chamber 20, and a reverse current absorber 18 provided in the negative electrode chamber 20, and the reverse current absorber 18. As illustrated in FIG. 95, the substrate 18a and the reverse current absorbing layer 18b formed on the substrate 18a are electrically connected to the cathode 21 and the reverse current absorbing layer 18b. The negative electrode chamber 20 further includes a current collector 23, a support 24 supporting the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the electrical power collector 23 and the negative electrode 21. The support body 24 is provided between the collector 23 and the partition 30. The current collector 23 is electrically connected to the negative electrode 21 via the metal elastic body 22. The partition 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition 30, the support body 24, the collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected to each other. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be connected indirectly via a current collector, a support, a metal elastic body, a partition, or the like. It is preferable that the whole surface of the cathode 21 is covered with a catalyst layer for the reduction reaction. In addition, in the form of electrical connection, the partition 30 and the support body 24, the support body 24 and the collector 23, the collector 23 and the metal elastic body 22 are respectively directly attached, and the metal elastic body 22 ) May be laminated on the cathode 21. Welding etc. are mentioned as a method of attaching these structural members directly to each other. In addition, the reverse current absorber 18, the negative electrode 21, and the current collector 23 may be collectively referred to as the negative electrode structure 40.

FIG. 92 is a cross-sectional view of two electrolytic cells 1 adjacent in the electrolytic cell 4. 93 shows the electrolytic cell 4. 94 shows a step of assembling the electrolytic cell 4. As shown in FIG. 92, the electrolytic cell 1, the cation exchange membrane 2, and the electrolytic cell 1 are arranged in series in this order. The ion exchange membrane 2 is arrange | positioned between the anode chamber of one electrolytic cell 1 and the cathode chamber of the other electrolytic cell 1 among two electrolytic cells which adjoin in an electrolytic cell. In other words, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are spaced apart by the cation exchange membrane 2. As shown in FIG. 93, the electrolytic cell 4 is composed of a plurality of electrolytic cells 1 connected in series via an ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 94, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series via an ion exchange membrane 2 and being connected by a press 5.

The electrolytic cell 4 has the positive terminal 7 and the negative terminal 6 connected to a power supply. The positive electrode 11 of the electrolytic cell 1 positioned at the shortest of the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4 is electrically connected to the positive electrode terminal 7. Among the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4, the negative electrode 21 of the electrolytic cell located at the end opposite to the positive electrode terminal 7 is electrically connected to the negative electrode terminal 6. The electric current at the time of electrolysis flows toward the negative electrode terminal 6 from the positive terminal 7 side via the positive electrode and the negative electrode of each electrolytic cell 1. Moreover, you may arrange | position the electrolytic cell (anode terminal cell) which has only an anode chamber, and the electrolytic cell (cathode terminal cell) which has only a cathode chamber in the both ends of the electrolytic cell 1 which connected. In this case, the positive terminal 7 is connected to the positive terminal cell disposed at one end thereof, and the negative terminal 6 is connected to the negative terminal cell arranged at the other end thereof.

In the case of electrolysis of brine, brine is supplied to each anode chamber 10, and pure or low concentration aqueous sodium hydroxide solution is supplied to the cathode chamber 20. Each liquid is supplied to each electrolytic cell 1 from electrolyte supply pipe (not shown) via electrolyte supply hose (not shown). In addition, electrolyte solution and the product by electrolysis are collect | recovered from an electrolyte collection pipe (not shown). In electrolysis, sodium ions in brine move from the anode chamber 10 of one electrolytic cell 1 through the ion exchange membrane 2 to the cathode chamber 20 of the neighboring electrolytic cell 1. Therefore, the current during electrolysis flows along the direction in which the electrolytic cells 1 are connected in series. That is, the current flows from the anode chamber 10 toward the cathode chamber 20 via the cation exchange membrane 2. By electrolysis of the brine, chlorine gas is produced on the anode 11 side, and sodium hydroxide (solute) and hydrogen gas are produced on the cathode 21 side.

(Positive room)

The anode chamber 10 includes a cathode 11 or an anode feeder 11. The term "feeder" as used herein means a deteriorated electrode (that is, an existing electrode), an electrode not coated with a catalyst, or the like. When the electrode for electrolysis in this embodiment is inserted in the anode side, 11 functions as a positive electrode feeder. When the electrode for electrolysis in this embodiment is not inserted in the anode side, 11 functions as an anode. In addition, the anode chamber 10 is disposed on an anode side electrolyte supply portion for supplying an electrolyte solution to the anode chamber 10 and an anode side electrolyte supply portion, and a baffle plate disposed to be substantially parallel or oblique with the partition wall 30. And it is preferable to have an anode side gas-liquid separation part arrange | positioned above the baffle plate and isolate | separates a gas from the electrolyte solution which gas mixed.

(anode)

When the electrode for electrolysis in this embodiment is not inserted in the anode side, the anode 11 is provided in the frame (namely, anode frame) of the anode chamber 10. As the anode 11, a metal electrode such as so-called DSA (registered trademark) can be used. DSA is a titanium-based electrode whose surface was covered with an oxide containing ruthenium, iridium and titanium.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Positive electrode feeder)

When the electrode for electrolysis in this embodiment is inserted in the anode side, the positive electrode feeder 11 is provided in the frame of the anode chamber 10. As the positive electrode feeder 11, a metal electrode such as DSA (registered trademark) or the like may be used, or titanium without a catalyst coating may be used. It is also possible to use DSA with a thinner catalyst coating thickness. Moreover, the used anode can also be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Anode-side electrolyte supply unit)

The anode-side electrolyte supply unit supplies the electrolyte solution to the anode chamber 10 and is connected to the electrolyte solution supply pipe. It is preferable that an anode side electrolyte supply part is arrange | positioned under the anode chamber 10. As an anode side electrolyte supply part, the pipe (dispersion pipe) etc. which have an opening part formed in the surface can be used, for example. It is more preferable that such a pipe is arrange | positioned in parallel with the bottom part 19 of an electrolysis cell along the surface of the anode 11. This pipe is connected to the electrolyte supply pipe (liquid supply nozzle) which supplies electrolyte solution in the electrolysis cell 1. The electrolyte solution supplied from the liquid supply nozzle is conveyed to the electrolysis cell 1 by the pipe, and is supplied to the inside of the anode chamber 10 from the opening provided in the surface of the pipe. By arranging the pipes parallel to the bottom portion 19 of the electrolytic cell along the surface of the anode 11, the electrolyte can be uniformly supplied into the anode chamber 10, which is preferable.

(Positive side gas-liquid separator)

It is preferable that the anode-side gas-liquid separator is disposed above the baffle plate. During electrolysis, the anode-side gas-liquid separator has a function of separating the generated gas such as chlorine gas and the electrolyte. In addition, unless otherwise indicated, an upper side means the upward direction in the electrolysis cell 1 of FIG. 91, and a lower side means the downward direction in the electrolysis cell 1 of FIG.

At the time of electrolysis, when the generated gas and electrolyte generated in the electrolytic cell 1 become mixed phase (gas-liquid mixed phase) and discharged out of the system, vibration occurs due to pressure fluctuation inside the electrolytic cell 1, and physical damage of the ion exchange membrane is prevented. I may cause it. In order to suppress this, it is preferable that the positive electrode side gas-liquid separation part for separating a gas and a liquid is provided in the electrolysis cell 1 of this embodiment. It is preferable that a defoaming plate for removing bubbles is provided in the anode-side gas-liquid separator. When a gas-liquid mixture flows through a vesicle plate, a bubble bursts and can be isolate | separated into electrolyte solution and gas. As a result, vibration during electrolysis can be prevented.

(Baffle version)

It is preferable that the baffle plate is disposed above the anode-side electrolyte supply portion, and is disposed substantially parallel to or inclined with the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. By providing the baffle plate, the electrolyte solution (salt water, etc.) can be circulated internally in the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged to be spaced apart from the space near the anode 11 and the space near the partition wall 30. From this viewpoint, the baffle plate is preferably provided so as to face each surface of the anode 11 and the partition wall 30. In the space near the anode partitioned by the baffle plate, electrolytic solution concentration (saline concentration) decreases as electrolysis proceeds, and product gas such as chlorine gas is generated. Thereby, the specific gravity difference of gas-liquid arises in the space near the anode 11 divided by the baffle plate, and the space near the partition 30. As shown in FIG. By using this, the internal circulation of the electrolyte solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolyte solution in the anode chamber 10 can be made more uniform.

Although not shown in FIG. 91, a current collector may be separately provided inside the positive electrode chamber 10. As such an electrical power collector, it can also be set as the material and structure similar to the electrical power collector of the negative electrode chamber mentioned later. In the anode chamber 10, the anode 11 itself can also function as a current collector.

(septum)

The partition 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition 30 may be called a separator and divides the anode chamber 10 and the cathode chamber 20. As the partition 30, a well-known thing can be used as a separator for electrolysis, For example, the partition which welded the plate which consists of nickel to the cathode side, and titanium to the anode side, etc. are mentioned.

(Cathode room)

The cathode chamber 20 functions as a cathode feeder when the electrode for electrolysis in the present embodiment is inserted on the cathode side, and when the electrode for electrolyte in the present embodiment is not inserted on the cathode side. , 21 functions as a cathode. When the reverse current absorber is provided, the negative electrode or the negative electrode feeder 21 and the reverse current absorber are electrically connected to each other. In addition, it is preferable that the cathode chamber 20 also has a cathode side electrolyte solution supply section and a cathode side gas-liquid separation section similarly to the anode chamber 10. In addition, description is abbreviate | omitted about the same thing as each part which comprises the anode chamber 10 among each site | part which comprises the cathode chamber 20. As shown in FIG.

(cathode)

When the electrode for electrolysis in this embodiment is not inserted in the cathode side, the cathode 21 is provided in the frame (namely, the cathode frame) of the cathode chamber 20. It is preferable that the negative electrode 21 has a catalyst layer which covers a nickel substrate and a nickel substrate. As a component of the catalyst layer on the nickel substrate, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd , Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho And metals such as Er, Tm, Yb and Lu, and oxides or hydroxides of the metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may give reduction process to the negative electrode 21 as needed. As the base material of the negative electrode 21, one in which nickel, nickel alloy, iron, or stainless steel is plated with nickel may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Cathode feeder)

When the electrode for electrolysis in this embodiment is inserted in the cathode side, the negative electrode feeder 21 is provided in the frame of the cathode chamber 20. The catalyst component may be coated on the negative electrode feeder 21. The catalyst component may be originally used as a negative electrode and remain. As components of the catalyst layer, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Metals, such as Tm, Yb, Lu, and the oxide or hydroxide of this metal are mentioned. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may use what plated nickel with nickel, nickel alloys, iron, or stainless steel which are not catalyst coated. As the base material of the negative electrode feeder 21, a plated nickel on nickel, a nickel alloy, iron or stainless may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

Reverse Current Absorption Layer

A material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected as the material of the reverse current absorbing layer. For example, nickel, iron, etc. are mentioned.

(Current collector)

The negative electrode chamber 20 preferably includes a current collector 23. This increases the current collecting effect. In the present embodiment, the current collector 23 is a porous plate, and is preferably disposed substantially parallel to the surface of the negative electrode 21.

The current collector 23 is preferably made of an electrically conductive metal such as nickel, iron, copper, silver, titanium, or the like. The current collector 23 may be a mixture of these metals, an alloy or a composite oxide. In addition, as long as it is a shape which functions as an electrical power collector, the shape of the electrical power collector 23 may be any shape, and plate-shaped or network-shaped may be sufficient as it.

(Metal elastomer)

By providing the metal elastic body 22 between the collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, The distance between each anode 11 and each cathode 21 can be shortened, and the voltage applied to the entire plurality of electrolytic cells 1 connected in series can be lowered. By lowering the voltage, the total consumption can be reduced. Moreover, when the metal elastic body 22 is provided and the laminated body containing the electrode for electrolysis in this embodiment is installed in an electrolytic cell, the said electrode for electrolysis by the pressure pressed by the metal elastic body 22 is carried out. Can be kept in a stable position.

As the metal elastic body 22, a spiral spring, a spring member such as a coil, a cushion mat, or the like can be used. As the metal elastic body 22, a suitable one can be appropriately adopted in consideration of a stress or the like which presses the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the collector 23 on the cathode chamber 20 side, or may be provided on the surface of the partition wall on the anode chamber 10 side. Usually, since both chambers are partitioned so that the cathode chamber 20 becomes smaller than the anode chamber 10, from the viewpoint of the strength of the frame or the like, the metal elastic body 22 is used for the current collector 23 of the cathode chamber 20. It is preferable to provide between and the cathode 21. Moreover, it is preferable that the metal elastic body 22 consists of metal which has electrical conductivity, such as nickel, iron, copper, silver, titanium.

(Support)

The negative electrode chamber 20 preferably includes a support 24 for electrically connecting the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently.

The support 24 is preferably made of a metal having electrical conductivity such as nickel, iron, copper, silver, titanium, or the like. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod, plate, or network. The support body 24 is plate-shaped, for example. The plurality of supports 24 are disposed between the partition wall 30 and the current collector 23. The plurality of supports 24 are arranged such that their respective surfaces are parallel to each other. The support body 24 is disposed substantially perpendicular to the partition wall 30 and the current collector 23.

(Anode side gasket, cathode side gasket)

It is preferable that the anode side gasket is arranged on the surface of the frame body constituting the anode chamber 10. It is preferable that the cathode side gasket is arrange | positioned at the surface of the frame body which comprises the cathode chamber 20. As shown in FIG. The anode side gasket which one electrolytic cell has, and the cathode side gasket of the electrolysis cell adjacent to this are connected so that the electrolytic cells may be clamped (refer FIG. 92). By these gaskets, when connecting a plurality of electrolytic cells 1 in series via the ion exchange membrane 2, airtightness can be provided to a connection location.

A gasket seals between an ion exchange membrane and an electrolysis cell. As a specific example of a gasket, a frame-shaped rubber sheet etc. in which the opening part was formed in the center are mentioned. The gasket is required to be resistant to corrosive electrolytes, generated gases and the like and to be used for a long time. Therefore, from the viewpoint of chemical resistance and hardness, vulcanized products, peroxide crosslinked products and the like of ethylene propylene diene rubber (EPDM rubber) and ethylene propylene rubber (EPM rubber) are usually used as the gasket. Moreover, the gasket which coat | covered the area | region (contact part) which contact | connects a liquid as needed with fluororesin, such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether polymer (PFA), can also be used. These gaskets should just have opening parts, respectively, so that the flow of electrolyte solution may not be disturbed, The shape is not specifically limited. For example, a frame-shaped gasket is bonded with an adhesive or the like along the circumferential edge of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20. For example, when connecting two electrolytic cells 1 via the ion exchange membrane 2 (refer FIG. 92), when each electrolytic cell 1 which bonded the gasket through the ion exchange membrane 2 is fastened, do. Thereby, it can suppress that an electrolyte solution, the alkali metal hydroxide produced by electrolysis, chlorine gas, hydrogen gas, etc. leak to the exterior of the electrolysis cell 1.

[Process using winding object]

The wound body in the present embodiment may be a wound body of an electrode for electrolysis, or may be a wound body of a laminate of an electrode for electrolysis and a new diaphragm. In the manufacturing method of the electrolytic cell which concerns on this embodiment, such a winding body is used. Although not limited to the following as a specific example of the process which uses a winding body, First, in the existing electrolytic cell, the fixed state of the adjacent electrolytic cell and ion exchange membrane by a press machine is canceled, and the said electrolytic cell and the ion exchange membrane between The method of forming a space | gap, then cancel | eliminating the wound state of the wound body of the electrolytic electrode, is inserted into the said space | gap, and each member is connected by a press machine, etc. are mentioned. In addition, when using the winding body of a laminated body, for example, forming a space | gap between an electrolysis cell and an ion exchange membrane as above, remove the existing ion exchange membrane used as an update object, and then, The method of inserting the thing which canceled the rolled state into the said space | gap, and connecting each member by a press machine, etc. are mentioned. By this method, the electrolytic electrode or the laminate can be disposed on the surface of the anode or cathode in the existing electrolytic cell, and the performance of the ion exchange membrane, the anode and / or the cathode can be updated.

As described above, in the present embodiment, it is preferable that the step of using the wound body has a step (B) of releasing the wound state of the wound body, and at least one surface of the positive electrode and the negative electrode after the step (B). It is more preferable to have a process (C) which arrange | positions an electrode for electrolysis or a laminated body on a phase.

Moreover, in this embodiment, it is preferable that the process of using a wound body has the process (A) of holding a electrolytic electrode or laminated body in the wound state, and obtaining a wound body. In step (A), the electrolytic electrode or the laminate itself may be wound into a wound body, or the electrolytic electrode or the laminate may be wound into a core to form a wound body. Although it does not specifically limit as a core which can be used here, For example, it has a substantially cylindrical shape, and the member of the magnitude | size according to an electrode for electrolysis or a laminated body can be used.

[Electrode Electrode]

In the present embodiment, the electrode for electrolysis is not particularly limited as long as it is used as the wound body, that is, it can be wound as described above. The electrode for electrolysis may function as a cathode in an electrolytic cell, or may function as an anode. In addition, regarding the material, shape, etc. of the electrode for electrolysis, an appropriate thing can be suitably selected in order to make a winding object in consideration of the process of using the winding object in this embodiment, the structure of an electrolytic cell, etc. Hereinafter, although the preferable aspect of the electrode for electrolysis in this embodiment is demonstrated, these are only illustrations of the preferable aspect in order to make it a winding object to the last, Electrolytic electrodes other than the aspect mentioned later can also be employ | adopted suitably. .

The electrode for electrolysis in this embodiment can obtain favorable handling property, and is a unit from a viewpoint of having favorable adhesive force, such as a diaphragm, such as an ion exchange membrane and a microporous membrane, a feeder (a deteriorated electrode and a catalyst uncoated electrode), etc. The force applied per mass and unit area is preferably 1.6 N / (mg · cm 2) or less, more preferably less than 1.6 N / (mg · cm 2), still more preferably less than 1.5 N / (mg · cm 2) More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred.

From the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and even more preferably 0.1 N / mg · cm 2 or more. More preferably, it is 0.14 N / (mg * cm <2>) or more. 0.2 N / (mg * cm <2>) or more is more preferable from a viewpoint of the ease of handling in a large size (e.g., size 1.5 m x 2.5 m).

The said applied force can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, arithmetic mean surface roughness, etc., for example. More specifically, for example, when the porosity is increased, the applied force tends to be small, and when the porosity is decreased, the applied force tends to be large.

In addition, good handling properties can be obtained, good adhesion to diaphragms such as ion exchange membranes and microporous membranes, deteriorated electrodes, catalyst uncoated feeders and the like, and from the viewpoint of economy, the mass per unit area is 48 mg / cm 2 or less. It is preferable, More preferably, it is 30 mg / cm <2> or less, More preferably, it is 20 mg / cm <2> or less, It is preferable that it is 15 mg / cm <2> or less from a comprehensive viewpoint which combined handling property, adhesiveness, and economics. Although a lower limit is not specifically limited, For example, it is about 1 mg / cm <2>.

The said mass per unit area can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, etc., for example. More specifically, for example, if the thickness is the same, the mass per unit area tends to be smaller when the porosity is increased, and the mass per unit area tends to be larger when the porosity is reduced.

The force applied can be measured by the following method (i) or (ii) and is as having described in the Example in detail. The force applied is also referred to as the value obtained by the measurement of the method (i) (also referred to as "the applied force 1"), and the value obtained by the measurement of the method (ii) (also referred to as the "force 2 applied"). ) May be the same or different, but any value is preferably less than 1.5 N / mg · cm 2.

[Method (i)]

Nickel plate obtained by blasting with alumina of particle number 320 (thickness 1.2 mm, width 200 mm) and an ion exchange membrane coated with inorganic particles and a binder on both sides of a membrane of a perfluorocarbon polymer into which an ion exchanger was introduced (horizontal 170 mm in length and the details of the ion-exchange membrane here, as described in the Example) and an electrode sample (130 mm in length) were laminated in this order, and this laminated body was fully immersed in pure water, and then laminated body. A sample for measurement is obtained by removing excess moisture adhering to the surface. In addition, the arithmetic mean surface roughness Ra of the nickel plate after a blasting process is 0.5-0.8 micrometer. The specific calculation method of arithmetic mean surface roughness Ra is as having described in the Example.

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were raised in 10 mm in the vertical direction. Measure the weight when This measurement is performed three times to calculate an average value.

The average value is divided by the area of the overlapped portion of the electrode sample and the ion exchange membrane and the mass of the electrode sample of the overlapped portion with the ion exchange membrane, and the force applied per unit mass and unit area (1) (N / mg · cm 2) To calculate.

The force (1) applied per unit mass and unit area obtained by the method (i) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is preferable that it is 1.6 N / (mg * cm <2>) or less from a viewpoint of having more, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more and more preferably 0.14 N / (mg · cm 2) and 0.2 N / (mg · cm 2) from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m). ) Is more preferable.

[Method (ii)]

The nickel plate (thickness 1.2 mm, width 200 mm, the same nickel plate as the method (i)) and the electrode sample (length 130 mm) obtained by blasting with alumina of particle number 320 were laminated in this order. After fully immersing the laminate with pure water, a sample for measurement is obtained by removing excess moisture adhering to the laminate surface. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were 10 mm in the vertical direction. The weight at the time of rise is measured. This measurement is performed three times to calculate an average value.

This average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate, and the mass of the electrode sample in the overlapped portion of the nickel plate, and the adhesive force 2 per unit mass and unit area (N / mg · cm 2) is obtained. Calculate.

The force (2) applied per unit mass and unit area obtained by the method (ii) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is preferable that it is 1.6 N / (mg * cm <2>) or less from a viewpoint of having more, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more, and even more preferably, from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m), still more preferably 0.14 N / (mg · cm 2) or more.

It is preferable that the electrolytic electrode in this embodiment contains an electrolytic electrode base material and a catalyst layer. Although the thickness (gauge thickness) of the said electrolytic electrode base material is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feedstock), and an electrode without a catalyst coating (grade 300 micrometers or less are preferable from a viewpoint of having a good adhesive force with the whole), and being rolled suitably, being able to bend it favorably, and facilitating handling in a large size (e.g., size 1.5 m x 2.5 m). 205 micrometers or less are more preferable, 155 micrometers or less are more preferable, 135 micrometers or less are still more preferable, 125 micrometers or less are still more preferable, 120 micrometers or less are still more preferable, 100 micrometers or less are further more preferable In addition, from a viewpoint of handling property and economical efficiency, 50 micrometers or less are further more preferable. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), From the viewpoint of having good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and also in a large size (e.g., size 1.5 m x 2.5 m). It is more preferable that it is 95% or more from the viewpoint of easy handling. The upper limit is 100%.

[Method (2)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the condition of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 280 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), It is preferable that it is 75% or more, and it is more preferable that it is 80% or more from the viewpoint of having favorable adhesive force, and being able to wind up in roll shape suitably, and bend | bending favorably. It is more preferable that it is 90% or more from a viewpoint that handling at a size (for example, size 1.5 m x 2.5 m) becomes easy. The upper limit is 100%.

[Method (3)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 145 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), It is preferable that it has a favorable adhesive force and is a porous structure from a viewpoint of the prevention of the residence of the gas which arises during electrolysis, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80% or less, still more preferably 20 to 75%.

In addition, an opening ratio is a ratio of an opening part per unit volume. The calculation method varies depending on whether the opening is also considered to submicron order or only the visible opening. In this embodiment, the porosity A can be calculated by the following formula by calculating the volume V from the values of the gauge thickness, the width, and the length of the electrode, and by measuring the weight W.

A = (1- (W / (V × ρ)) × 100

ρ is the density (g / cm 3) of the material of the electrode. For example, nickel is 8.908 g / cm 3 and titanium is 4.506 g / cm 3. The adjustment of the porosity is to change the area punching the metal per unit area if the punching metal, change the SW (short diameter), LW (long diameter), the feeding value if the expanded metal, the mesh diameter of the metal fiber, By changing the number of meshes, changing the pattern of the photoresist to be used for electroforming, changing the metal fiber diameter and fiber density for nonwoven fabrics, and changing the mold for forming the voids for the foamed metal, etc. I can adjust it.

Hereinafter, more specific embodiment of the electrode for electrolysis in this embodiment is demonstrated.

It is preferable that the electrolytic electrode which concerns on this embodiment contains an electrolytic electrode base material and a catalyst layer. The catalyst layer may be composed of a plurality of layers as described below or may have a single layer structure.

As illustrated in FIG. 96, the electrolytic electrode 100 according to the present embodiment includes a pair of first layers 20 covering both surfaces of the electrolytic electrode substrate 10 and the electrolytic electrode substrate 10. It is provided. It is preferable that the 1st layer 20 coat | covers the electrolytic electrode base material 10 whole. As a result, the catalytic activity and durability of the electrode for electrolysis tends to be improved. In addition, the first layer 20 may be laminated only on one surface of the electrode base 10 for electrolysis.

96, the surface of the 1st layer 20 may be coat | covered with the 2nd layer 30. As shown in FIG. The second layer 30 preferably covers the entire first layer 20. In addition, only one surface of the first layer 20 may be laminated on the second layer 30.

(Electrode base for electrolysis)

The electrolytic electrode substrate 10 is not particularly limited, but a valve metal such as nickel, nickel alloy, stainless steel or titanium may be used, and at least one selected from nickel (Ni) and titanium (Ti) may be used. It is preferable to include the element of a species.

When stainless steel is used in a high concentration aqueous alkali solution, considering that iron and chromium are eluted, and that the electrical conductivity of stainless steel is about 1/10 of nickel, the electrolytic electrode substrate includes nickel (Ni). The substrate is preferred.

In addition, when the electrolytic electrode base material 10 is used in the chlorine gas generation | occurence atmosphere in the high concentration saline solution near saturation, it is preferable that a material is titanium with high corrosion resistance.

There is no restriction | limiting in particular in the shape of the electrode base material 10 for electrolysis, An appropriate shape can be selected according to the objective. As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used. Especially, a punching metal or an expanded metal is preferable. In addition, electroforming is a technique which manufactures a metal thin film of a precise pattern by combining photolithography and an electroplating method. It is a method of pattern-forming with a photoresist on a board | substrate, electroplating to the part which is not protected by a resist, and obtaining metal foil.

The shape of the electrode base material for electrolysis has suitable specifications depending on the distance between the anode and the cathode in the electrolytic cell. Although not particularly limited, in the case where the anode and the cathode have a finite distance, an expanded metal or a punched metal shape can be used, and in the case of a so-called zero gap electrolytic cell in which the ion exchange membrane and the electrode are in contact, a woven mesh woven with fine lines , Wire mesh, foamed metal, metal nonwoven fabric, expanded metal, punched metal, metal porous foil and the like can be used.

Examples of the electrode base 10 for electrolysis include a metal porous foil, a wire mesh, a metal nonwoven fabric, a punching metal, an expanded metal or a foamed metal.

As a board | plate material before processing with a punching metal and an expanded metal, the board | plate material roll-molded, electrolytic foil, etc. are preferable. It is preferable that the electrolytic foil is further plated with the same element as the base material as post-treatment to form irregularities on one or both surfaces.

In addition, it is preferable that the thickness of the electrolytic electrode base material 10 is 300 micrometers or less as mentioned above, It is more preferable that it is 205 micrometers or less, It is more preferable that it is 155 micrometers or less, It is further more preferable that it is 135 micrometers or less, 125 It is still more preferable that it is micrometer or less, It is still more preferable that it is 120 micrometers or less, It is still more preferable that it is 100 micrometers or less, It is further more preferable that it is 50 micrometers or less from a viewpoint of handling property and economy. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In the electrode base for electrolysis, it is preferable to relieve the residual stress at the time of processing by annealing the electrode base for electrolysis in an oxidizing atmosphere. Moreover, in order to improve the adhesiveness with the catalyst layer coat | covered with the said surface, the surface of an electrolytic electrode base material uses unevenness | corrugation using a steel grid, alumina powder, etc., and it is preferable to increase a surface area by acid treatment after that. Do. Or it is preferable to plating by the same element as a base material, and to increase a surface area.

In order to make the surface of the 1st layer 20 and the electrode base material 10 for electrolysis adhere to the electrode base material 10 for electrolysis, it is preferable to perform the process which increases a surface area. Examples of the treatment for increasing the surface area include a blast treatment using a cut wire, a steel grid, an alumina grid, and the like, an acid treatment using sulfuric acid or hydrochloric acid, a plating treatment using the same element as the substrate, and the like. Although arithmetic mean surface roughness Ra of the surface of a base material is not specifically limited, 0.05 micrometer-50 micrometers are preferable, 0.1-10 micrometers is more preferable, 0.1-8 micrometers is still more preferable.

Next, the case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

In FIG. 96, the first layer 20 serving as the catalyst layer contains at least one oxide of ruthenium oxide, iridium oxide and titanium oxide. Ruthenium oxide RuO _2, etc., may be mentioned. IrO ₂ etc. are mentioned as an iridium oxide. Examples of titanium oxides include TiO ₂ . The first layer 20 preferably contains two kinds of oxides of ruthenium oxide and titanium oxide, or three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide. Thereby, the 1st layer 20 becomes a more stable layer, and also adhesiveness with the 2nd layer 30 improves more.

In the case where the first layer 20 includes two kinds of oxides of ruthenium oxide and titanium oxide, titanium contained in the first layer 20 with respect to one mole of ruthenium oxide included in the first layer 20. It is preferable that it is 1-9 mol, and, as for an oxide, it is more preferable that it is 1-4 mol. By setting the composition ratio of the two kinds of oxides in this range, the electrolytic electrode 100 exhibits excellent durability.

When the first layer 20 includes three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide, the first layer 20 is included in the first layer 20 with respect to one mole of ruthenium oxide contained in the first layer 20. It is preferable that it is 0.2-3 mol, and, as for the iridium oxide used, it is more preferable that it is 0.3-2.5 mol. Moreover, it is preferable that it is 0.3-8 mol, and, as for 1 mol of titanium oxide contained in the 1st layer 20 with respect to 1 mol of ruthenium oxide contained in the 1st layer 20, it is more preferable. By making the composition ratio of three types of oxides into this range, the electrode 100 for electrolysis shows the outstanding durability.

When the 1st layer 20 contains at least 2 types of oxide chosen from a ruthenium oxide, an iridium oxide, and a titanium oxide, it is preferable that these oxides form a solid solution. By forming the oxide solid solution, the electrolytic electrode 100 exhibits excellent durability.

In addition to the above composition, as long as it contains at least one oxide of ruthenium oxide, iridium oxide and titanium oxide, those having various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like, referred to as DSA (registered trademark), may be used as the first layer 20.

The first layer 20 does not need to be a single layer, but may include a plurality of layers. For example, the first layer 20 may include a layer containing three kinds of oxides and a layer containing two kinds of oxides. 0.05-10 micrometers is preferable and, as for the thickness of the 1st layer 20, 0.1-8 micrometers is more preferable.

(2nd floor)

It is preferable that the 2nd layer 30 contains ruthenium and titanium. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

It is preferable that the 2nd layer 30 contains palladium oxide, the solid solution of palladium oxide, and platinum, or the alloy of palladium and platinum. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

The longer the longer the thickness of the second layer 30 can maintain the electrolytic performance, the thickness of the second layer 30 is preferably 0.05 to 3 m.

Next, the case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

As a component of the first layer 20 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal include at least one kind, the alloy containing the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide and the platinum group metal is platinum, palladium, rhodium, It is preferable to contain at least 1 type of platinum group metal among ruthenium and iridium.

As a platinum group metal, it is preferable to contain platinum.

It is preferable that a platinum group metal oxide contains ruthenium oxide.

It is preferable that a platinum group metal hydroxide contains a ruthenium hydroxide.

As a platinum group metal alloy, it is preferable to include the alloy of platinum, nickel, iron, and cobalt.

Moreover, it is preferable to contain the oxide or hydroxide of a lanthanoid element as a 2nd component as needed. As a result, the electrolytic electrode 100 exhibits excellent durability.

The oxide or hydroxide of the lanthanoid-based element preferably contains at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium.

Moreover, it is preferable to contain the oxide or hydroxide of a transition metal as a 3rd component as needed.

By adding the third component, the electrolytic electrode 100 exhibits more excellent durability and can reduce the electrolytic voltage.

Examples of preferred combinations include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + platinum + palladium Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium + Sulfur, Ruthenium + Lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + samarium + cobalt, ruthenium + samarium + gallium, ruthenium + samarium + gallium, ruthenium + Samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + Nickel + palladium, bag Gold + nickel + ruthenium, an alloy of platinum and nickel, an alloy of platinum and cobalt, an alloy of platinum and iron, and the like.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal are not included, the main component of the catalyst is preferably nickel element.

It is preferable to contain at least 1 sort (s) among nickel metal, oxide, and hydroxide.

You may add a transition metal as a 2nd component. As a 2nd component to add, it is preferable to contain at least 1 type of element among titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon.

As a preferable combination, nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, etc. are mentioned.

If necessary, an intermediate layer can be formed between the first layer 20 and the electrolytic electrode substrate 10. By providing the intermediate layer, the durability of the electrolytic electrode 100 can be improved.

As an intermediate | middle layer, what has affinity for both the 1st layer 20 and the electrode base material 10 for electrolysis is preferable. As the intermediate layer, nickel oxide, platinum group metal, platinum group metal oxide, and platinum group metal hydroxide are preferable. As an intermediate | middle layer, it can form by apply | coating and baking the solution containing the component which forms an intermediate | middle layer, and can also form a surface oxide layer by heat-processing a base material at 300-600 degreeC in air atmosphere. In addition, it can form by a well-known method, such as a thermal spraying method and an ion plating method.

(2nd floor)

As the components of the first layer 30 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included. Examples of preferred combinations of the elements included in the second layer include combinations exemplified in the first layer. The combination of a 1st layer and a 2nd layer may be a combination with the same composition, and a composition ratio differs, and the combination of a different composition may be sufficient as it.

As thickness of a catalyst layer, the sum total of the formed catalyst layer and the intermediate | middle layer has preferable 0.01 micrometer-20 micrometers. If it is 0.01 micrometer or more, it can fully function as a catalyst. If it is 20 micrometers or less, a strong catalyst layer can be formed with little fall-out from a base material. 0.05 micrometers-15 micrometers are more preferable. More preferably, they are 0.1 micrometer-10 micrometers. More preferably, they are 0.2 micrometer-8 micrometers.

As thickness of an electrode, ie, the thickness of the sum total of an electrolytic electrode base material and a catalyst layer, 315 micrometers or less are preferable, 220 micrometers or less are more preferable, 170 micrometers or less are more preferable from a viewpoint of handling property of an electrode, 150 The thickness is even more preferable, 145 µm or less is particularly preferable, 140 µm or less is still more preferable, 138 µm or less is even more preferable, and 135 µm or less is even more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, it is preferable that it is 130 micrometers or less from a viewpoint similar to the above, More preferably, it is less than 130 micrometers, More preferably, it is 115 micrometers or less, More preferably, it is 65 micrometers or less. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, the thickness of an electrode can be calculated | required by measuring with a dejimatic thickness gauge (Mitsutoyo Corporation, minimum display 0.001 mm). The thickness of the electrode base material for electrodes is measured similarly to electrode thickness. The catalyst layer thickness can be obtained by subtracting the thickness of the electrode base material for electrolysis from the electrode thickness.

In the present embodiment, from the viewpoint of securing sufficient electrolytic performance, the electrode for electrolysis is Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y , Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd It is preferred to include at least one catalyst component selected from the group consisting of Pm, Sm, Eu, Gd, Tb and Dy.

In the present embodiment, the electrode for electrolysis can obtain better handling property as long as it is an electrode having a large elastic deformation region, and has better adhesion force such as a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, a catalyst-free feeder, and the like. From the viewpoint of having a thickness, the thickness of the electrode for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, still more preferably 170 µm or less, even more preferably 150 µm or less, and particularly 145 µm or less. Preferably, 140 micrometers or less are further more preferable, 138 micrometers or less are further more preferable, 135 micrometers or less are further more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, from a viewpoint similar to the above, 130 micrometers or less are preferable, less than 130 micrometers are more preferable, 115 micrometers or less are more preferable, and 65 micrometers or less are still more preferable. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, in this embodiment, a "elastic deformation area | region is wide" means that it is difficult to produce the curvature resulting from winding after winding an electrode for electrolysis to make a winding body, and canceling a wound state. In addition, the thickness of an electrode for electrolysis means the thickness which combined the electrode base material for electrolysis and a catalyst layer, when including the catalyst layer mentioned later.

(Method for producing electrode for electrolysis)

Next, one Embodiment of the manufacturing method of the electrolytic electrode 100 is described in detail.

In the present embodiment, the first layer 20, preferably the second layer (on the electrode base material for electrolysis) is performed by a method such as baking (pyrolysis) of the coating film in an oxygen atmosphere or ion plating, plating, thermal spraying or the like. By forming 30), the electrode 100 for electrolysis can be manufactured. In this manufacturing method of the present embodiment, high productivity of the electrode 100 for electrolysis can be realized. Specifically, a catalyst layer is formed on the electrode base material for electrolysis by a coating step of applying a coating liquid containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing pyrolysis. Pyrolysis means here that the metal salt used as a precursor is heated and decomposed | disassembled into a metal or metal oxide and gaseous substance. Although decomposition products differ depending on the metal species used, the kind of salt, and the atmosphere in which pyrolysis is performed, most metals tend to form oxides in an oxidizing atmosphere. In the industrial production process of electrodes, pyrolysis is usually carried out in air, and in most cases metal oxides or metal hydroxides are formed.

(Formation of the first layer of the anode)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved at least 1 sort (s) of metal salt of ruthenium, iridium, and titanium to an electrolytic electrode base material, and thermally decomposes (baking) in presence of oxygen. The content of ruthenium, iridium and titanium in the first coating liquid is approximately the same as that of the first layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of the second layer)

The 2nd layer 30 is formed as needed, for example, apply | coating the solution containing a palladium compound and a platinum compound, or the solution (2nd coating liquid) containing a ruthenium compound and a titanium compound on the 1st layer 20 After that, it is obtained by pyrolysis in the presence of oxygen.

(Formation of First Layer of Cathode by Pyrolysis)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved the metal salt of various combinations to the electrode base material for electrolysis, and thermally decomposing (baking) in presence of oxygen. The content rate of the metal in a 1st coating liquid is substantially the same as the 1st layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of intermediate layer)

An intermediate | middle layer is formed as needed, for example, is obtained by apply | coating the solution (2nd coating liquid) containing a palladium compound or a platinum compound on a base material, and then thermally decomposing in presence of oxygen. Alternatively, the nickel oxide intermediate layer may be formed on the surface of the substrate only by heating the substrate without applying the solution.

(Formation of First Layer of Cathode by Ion Plating)

The first layer 20 may be formed by ion plating.

As an example, the method of fixing a base material in a chamber, and irradiating an electron beam to a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and ruthenium is deposited on the substrate as ruthenium oxide.

(Formation of First Layer of Cathode by Plating)

The first layer 20 can also be formed by a plating method.

As an example, when a base material is used as a cathode and electrolytic plating is performed in the electrolyte solution containing nickel and tin, alloy plating of nickel and tin can be formed.

(Formation of First Layer of Cathode by Thermal Spray)

The first layer 20 can also be formed by thermal spraying.

As an example, by spraying nickel oxide particles on a substrate, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed.

[Laminated body]

The electrode for electrolysis in this embodiment can be used as a laminated body with septum, such as an ion exchange membrane and a microporous membrane. That is, the laminated body in this embodiment contains an electrode for electrolysis and a new diaphragm. The new diaphragm is not particularly limited as long as it is separate from the diaphragm in the existing electrolytic cell, and various known diaphragms can be applied. The new diaphragm may be the same as the diaphragm in the existing electrolytic cell in terms of material, shape, physical properties, and the like.

Hereinafter, the ion exchange membrane which concerns on one aspect of a diaphragm is explained in full detail.

[Ion exchange membrane]

The ion exchange membrane is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various ion exchange membranes can be applied. In this embodiment, it is preferable to use the membrane main body containing the hydrocarbon type polymer or fluorine-containing polymer which has an ion exchange group, and the ion exchange membrane which has a coating layer formed on at least one surface of this membrane main body. In addition, it is preferable that the coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is 0.1-10 m 2 / g. The ion-exchange membrane of such a structure has little influence on the electrolytic performance by the gas which generate | occur | produces during electrolysis, and it tends to exhibit stable electrolytic performance.

The membrane of the perfluorocarbon polymer into which the ion exchange group is introduced is a sulfonic acid layer having an ion exchange group derived from a sulfo group (group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and an ion exchange group derived from a carboxyl group. It is provided with either a carboxylic sancheung having a - (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). In view of strength and dimensional stability, it is preferable to further have a reinforcing core material.

The inorganic particles and the binder will be described in detail in the description section of the coating layer below.

FIG. 97 is a schematic sectional view showing one embodiment of an ion exchange membrane. FIG. The ion exchange membrane 1 has a membrane main body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group, and coating layers 11a and 11b formed on both surfaces of the membrane main body 10.

In the ion exchange membrane 1, the membrane main body 10 is a sulfonic acid layer 3 having an ion exchange group derived from a sulfo group (a group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and ions derived from a carboxyl group. exchanger has a strength and dimensional stability are enhanced by the carboxylic sancheung 2 provided, and the reinforcement core (4) having a (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). Since the ion exchange membrane 1 is provided with the sulfonic acid layer 3 and the carboxylic acid layer 2, it is suitably used as a cation exchange membrane.

In addition, the ion exchange membrane may have only one of a sulfonic acid layer and a carboxylic acid layer. In addition, the ion exchange membrane does not necessarily need to be reinforced by the reinforcing core, and the arrangement state of the reinforcing core is not limited to the example of FIG. 97.

(The membrane body)

First, the membrane main body 10 constituting the ion exchange membrane 1 will be described.

The membrane main body 10 may have a function of selectively permeating cations, and may include a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group. The structure and the material thereof are not particularly limited, and a suitable one can be appropriately selected. have.

The hydrocarbon-based polymer or fluorine-containing polymer having an ion exchange group in the membrane main body 10 can be obtained from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange precursor which can be an ion-exchange group, for example, by hydrolysis or the like. Specifically, for example, the main chain is made of a fluorinated hydrocarbon, and has a group (ion exchanger precursor) which can be converted into an ion exchanger by hydrolysis or the like as a pendant side chain, and also a polymer which can be melt processed (hereinafter referred to as "fluorine-containing polymer). (a) ") to produce the precursor of the membrane main body 10, and then convert the ion exchanger precursor into the ion exchanger to obtain the membrane main body 10.

The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the third group below. have. Moreover, it can also manufacture by the homopolymerization of 1 type of monomers chosen from any of the following 1st group, the following 2nd group, and the following 3rd group.

As a monomer of a 1st group, a vinyl fluoride compound is mentioned, for example. Examples of the vinyl fluoride compound include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and the like. In particular, when the ion exchange membrane is used as the alkali electrolytic membrane, the vinyl fluoride compound is preferably a perfluoro monomer, and is perfluoro selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Monomer is preferred.

As a monomer of a 2nd group, the vinyl compound which has a functional group which can be converted into a carboxylic acid type ion exchange group (carboxylic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted to a carboxylic acid group, for example, and the like can be _{CF 2 = CF (OCF 2 CYF} ) s -O (CZF) t monomers represented by -COOR (wherein, s is 0 An integer of -2, t represents an integer of 1 to 12, Y and Z each independently represents F or CF ₃ , and R represents a lower alkyl group, for example, a lower alkyl group is an alkyl group having 1 to 3 carbon atoms. .).

Among these, CF is _{2 = CF (OCF 2 CYF)} n -O (CF 2) _m -COOR compound represented by are preferred. Here n represents an integer of 0 to 2, m represents an integer of 1 to 4, Y represents F or CF ₃ , and R represents CH ₃ , C ₂ H ₅ or C ₃ H ₇ .

When the ion exchange membrane is used as a cation exchange membrane for alkali electrolysis, it is preferable to use at least a perfluoro compound as the monomer. However, since the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis, the alkyl group ( R) may not be a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

As a monomer of a 2nd group, the monomer shown below is more preferable among the above.

CF ₂ = CFOCF ₂ -CF (CF ₃ ) OCF ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CF [OCF ₂ -CF (CF ₃ )] ₂ O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₃ COOCH ₃ .

As a monomer of a 3rd group, the vinyl compound which has a functional group which can be converted into a sulfone type ion exchange group (sulfonic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted into a sulfonic acid is, for example, CF ₂ = a monomer represented by the _{CFO-X-CF 2 -SO 2} F are preferred (wherein, X represents an alkylene group of a perfluoroalkyl.). As these specific examples, the monomer etc. which are shown below are mentioned.

CF ₂ = CFOCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CF (CF ₂ ) ₂ SO ₂ F,

CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₂ OCF ₃ ) OCF ₂ CF ₂ SO ₂ F.

Among these, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F are more preferable.

The copolymer obtained from these monomers can be manufactured by the polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, especially the general polymerization method used with respect to tetrafluoroethylene. For example, in the non-aqueous method, inert solvents such as perfluorohydrocarbon and chlorofluorocarbon are used, and in the presence of radical polymerization initiators such as perfluorocarbon peroxide and azo compound, the temperature is 0 to 200 캜 and the pressure is 0.1 to 0.1. The polymerization reaction can be carried out under the condition of 20 MPa.

In the said copolymerization, the kind and ratio of the combination of the said monomers are not specifically limited, It selects according to the kind and quantity of the functional group to provide to the fluorine-containing polymer obtained. For example, in the case of using a fluorine-containing polymer containing only a carboxylic acid group, at least one monomer may be selected and copolymerized from the first group and the second group, respectively. In the case of using a fluorine-containing polymer containing only a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group and the third group, respectively. In the case of using a fluorine-containing polymer having a carboxylic acid group and a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group, the second group, and the third group, respectively. In this case, the target fluorine-containing polymer can also be obtained by separately polymerizing the copolymer composed of the first group and the second group and the copolymer composed of the first group and the third group, and then mixing the copolymer separately. . Moreover, although the mixing ratio of each monomer is not specifically limited, When increasing the quantity of functional groups per unit polymer, what is necessary is just to increase the ratio of the monomer chosen from the said 2nd group and the 3rd group.

Although the total ion exchange capacity of a fluorine-containing copolymer is not specifically limited, It is preferable that it is 0.5-2.0 mg equivalent / g, and it is more preferable that it is 0.6-1.5 mg equivalent / g. Here, total ion exchange capacity means the equivalent of the exchanger per unit weight of dry resin, and can be measured by neutralization titration etc.

In the membrane main body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorine-containing polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorine-containing polymer having a carboxylic acid group are laminated. . By using this layer structure as the membrane main body 10, the selective permeability of cations such as sodium ions can be further improved.

In the case where the ion exchange membrane 1 is disposed in the electrolytic cell, the sulfonic acid layer 3 is usually disposed on the anode side of the electrolytic cell and the carboxylic acid layer 2 on the cathode side of the electrolytic cell.

It is preferable that the sulfonic acid layer 3 is comprised from the material with low electrical resistance, and it is preferable that a film thickness is thicker than the carboxylic acid layer 2 from a viewpoint of film strength. The film thickness of the sulfonic acid layer 3 becomes like this. Preferably it is 2-25 times of the carboxylic acid layer 2, More preferably, it is 3-15 times.

It is preferable that the carboxylic acid layer 2 has high anion exclusion property even if it is thin. Anion-exclusion here means the property which wants to interrupt the invasion and permeation | transmission of anion to the ion exchange membrane 1. In order to improve anion exclusion, disposing a carboxylic acid layer having a small ion exchange capacity with respect to the sulfonic acid layer is effective.

As the fluorine-containing polymer used for the sulfonic acid layer 3, for example, a polymer obtained by using CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F as the third group of monomers is suitable.

Carboxylic acids referred to as the fluorine-based polymer for use in sancheung (2) is, for example, as monomers of group 2 _{CF 2 = CFOCF 2 CF (CF} 2) O (CF 2) a polymer obtained by using ₂ COOCH ₃ are suitable.

(Coating layer)

It is preferable that an ion exchange membrane has a coating layer on at least one surface of a membrane main body. 97, in the ion exchange membrane 1, the coating layers 11a and 11b are formed on both surfaces of the membrane main body 10, respectively.

The coating layer includes inorganic particles and a binder.

As for the average particle diameter of an inorganic particle, it is more preferable that it is 0.90 micrometer or more. If the average particle diameter of the inorganic particles is 0.90 µm or more, the durability against impurities as well as gas adhesion is greatly improved. In other words, a particularly significant effect is obtained by increasing the average particle diameter of the inorganic particles and by satisfying the above-described specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by crushing gemstones can be used. Preferably, the inorganic particles obtained by gemstone grinding can be suitably used.

In addition, the average particle diameter of an inorganic particle can be 2 micrometers or less. If the average particle diameter of an inorganic particle is 2 micrometers or less, it can prevent that a film | membrane is damaged by an inorganic particle. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 µm.

Here, an average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation).

It is preferable that the shape of an inorganic particle is an irregular shape. Resistance to impurities is further improved. In addition, the particle size distribution of the inorganic particles is preferably wide.

It is preferable that an inorganic particle contains at least 1 sort (s) of inorganic substance chosen from the group which consists of an oxide of a group IV element of a periodic table, a nitride of a group IV element of a periodic table, and a carbide of a group IV element of a periodic table. More preferably, they are particles of zirconium oxide from the viewpoint of durability.

It is preferable that this inorganic particle is an inorganic particle manufactured by crushing the gemstone of an inorganic particle, or it is preferable to make spherical particle | grains of the uniform diameter of particle | grains into an inorganic particle by melting and refine | purifying the gemstone of an inorganic particle.

Examples of the raw material grinding method include, but are not particularly limited to, ball mills, bead mills, colloid mills, conical mills, disc mills, edge mills, milling mills, hammer mills, pellet mills, VSI mills, willy mills, roller mills, and jet mills. Etc. can be mentioned. Moreover, it is preferable to wash | clean after grinding | pulverization, and it is preferable to be acid-processed at that time. As a result, impurities such as iron adhering to the surface of the inorganic particles can be reduced.

The coating layer preferably comprises a binder. A binder is a component which keeps inorganic particle on the surface of an ion exchange membrane, and comprises a coating layer. It is preferable that a binder contains a fluorine-containing polymer from a viewpoint of resistance to electrolyte solution or the product by electrolysis.

As a binder, it is more preferable that it is a fluorine-containing polymer which has a carboxylic acid group or a sulfonic acid group from a tolerance with respect to the electrolyte solution and the product by electrolysis, and adhesiveness to the surface of an ion exchange membrane. When forming a coating layer on the layer (sulfonic acid layer) containing a fluorine-containing polymer which has a sulfonic acid group, it is more preferable to use the fluorine-containing polymer which has a sulfonic acid group as a binder of this coating layer. Moreover, when forming a coating layer on the layer (carboxylic acid layer) containing the fluorine-containing polymer which has a carboxylic acid group, it is more preferable to use the fluorine-containing polymer which has a carboxylic acid group as a binder of this coating layer.

It is preferable that it is 40-90 mass%, and, as for content of an inorganic particle in a coating layer, it is more preferable that it is 50-90 mass%. Moreover, it is preferable that it is 10-60 mass%, and, as for content of a binder, it is more preferable that it is 10-50 mass%.

The distribution density of the coating layer in the ion exchange membrane is preferably 0.05 to 2 mg per cm 2. In addition, when an ion exchange membrane has a concave-convex shape on the surface, it is preferable that the distribution density of a coating layer is 0.5-2 mg per cm <2>.

It does not specifically limit as a method of forming a coating layer, A well-known method can be used. For example, the method of apply | coating the coating liquid which disperse | distributed inorganic particle to the solution containing a binder by spray etc. is mentioned.

(Reinforced heartwood)

It is preferable that the ion exchange membrane has a reinforcing core material disposed inside the membrane body.

The reinforcing core is a member for enhancing the strength and dimensional stability of the ion exchange membrane. By arrange | positioning a reinforcing core material inside a membrane main body, especially expansion and contraction of an ion exchange membrane can be controlled to a desired range. Such an ion exchange membrane can maintain excellent dimensional stability for a long time without being stretched more than necessary in electrolysis or the like.

The configuration of the reinforcing core is not particularly limited, and may be formed by spinning a yarn called reinforcing yarn, for example. The reinforcement yarn mentioned here is a member which constitutes a reinforcing core material, which can impart desired dimensional stability and mechanical strength to the ion exchange membrane, and refers to a yarn that can stably exist in the ion exchange membrane. By using the reinforcing core material which radiated such reinforcement yarn, further excellent dimensional stability and mechanical strength can be provided to the ion exchange membrane.

The material of the reinforcing core material and the reinforcing yarn used for this is not particularly limited, but it is preferable that the material is resistant to acids, alkalis, or the like. desirable.

Examples of the fluorine-containing polymer used in the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether polymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetra Fluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, vinylidene fluoride polymer (PVDF), and the like. Among these, it is preferable to use the fiber which consists of polytetrafluoroethylene from a heat resistant and chemical resistant viewpoint especially.

The diameter of the reinforcing sand used for the reinforcing core is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The weave density (number of insertion lines per unit length) is preferably 5 to 50 lines / inch. The form of the reinforcing core is not particularly limited, and for example, a woven fabric, a nonwoven fabric, a knitted fabric, or the like is used, but it is preferably a form of a woven fabric. In addition, the thickness of the woven fabric is preferably 30 to 250 m, more preferably 30 to 150 m.

As the woven fabric or knitted fabric, monofilament, multifilament or yarns, slit yarns, and the like thereof can be used, and the weaving method can use various weaving methods such as plain weave, leno weave, knitting, cord weave, and seerker.

The weaving method and arrangement of the reinforcing core material in the membrane main body are not particularly limited and can be appropriately arranged in consideration of the size and shape of the ion exchange membrane, the desired physical properties and the use environment for the ion exchange membrane, and the like.

For example, the reinforcing core may be disposed along a predetermined direction of the membrane body, but from the viewpoint of dimensional stability, the reinforcing core is disposed along the predetermined first direction, and a second direction substantially perpendicular to the first direction is provided. Therefore, it is preferable to arrange a separate reinforcing core material. By arranging the plurality of reinforcing cores so as to run substantially straight inside the longitudinal membrane body of the membrane body, further superior dimensional stability and mechanical strength can be imparted in multiple directions. For example, an arrangement for weaving the reinforcing core material (warp) disposed along the longitudinal direction and the reinforcing core material (weft) arranged along the transverse direction on the surface of the membrane body is preferable. Lion weaved by inserting the same number of wefts into the weaving plain weave by twisting and inserting warp and weft alternately, or by weaving two warp and leno weaving by twisting two warp and two or several lines. It is more preferable to use a woven fabric (a loom) from the viewpoint of dimensional stability, mechanical strength, and ease of manufacture.

In particular, it is preferable that the reinforcing core is disposed along both directions of the MD direction (Machine Direction direction) and the TD direction (Transverse Direction direction) of the ion exchange membrane. That is, it is preferable to be woven in the MD direction and the TD direction. Here, MD direction means the direction (flow direction) in which a membrane main body and various core materials (for example, a reinforced core material, a reinforcement yarn, a sacrificial yarn etc. mentioned later) are conveyed in the manufacturing process of the ion exchange membrane mentioned later, and a TD direction is It refers to a direction approximately perpendicular to the MD direction. The yarn woven along the MD direction is called MD yarn, and the yarn woven along the TD direction is called TD yarn. Usually, the ion exchange membrane used for electrolysis is rectangular, and a longitudinal direction becomes MD direction, and the width direction becomes a TD direction in many cases. By weaving the reinforced MD core material and the reinforced TD core material, it is possible to give even more excellent dimensional stability and mechanical strength in multiple directions.

The spacing of the reinforcing cores is not particularly limited and can be appropriately arranged in consideration of desired physical properties, use environment, and the like for the ion exchange membrane.

The opening ratio of the reinforcing core material is not particularly limited, and is preferably 30% or more, more preferably 50% or more and 90% or less. The opening ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane.

The opening ratio of the reinforcing core is the total area (B) of the surface through which substances such as ions (electrolyte and cation (for example, sodium ions) contained) in the area (A) of either surface of the membrane body can pass. The ratio of (B / A). The total area (B) of the surface through which substances such as ions can pass can be referred to as the total area of the region where cations, electrolytes, and the like are not blocked by the reinforcing core included in the ion exchange membrane.

FIG. 98 is a schematic view for explaining the aperture ratio of the reinforcing core constituting the ion exchange membrane. FIG. FIG. 98 enlarges a part of the ion exchange membrane and shows only the arrangement of the reinforcing core materials 21 and 22 in the region, and the illustration of the other members is omitted.

The total area C of the reinforcement core from the area A of the region including the area of the reinforcement core, which is also surrounded by the reinforcement core 21 arranged in the longitudinal direction and the reinforcement core 22 arranged in the horizontal direction. By subtracting, the total area B of the area through which substances such as ions in the area A of the area can pass can be obtained. That is, an opening ratio can be calculated | required by following formula (I).

Aperture ratio = (B) / (A) = ((A)-(C)) / (A). (I)

Among the reinforcing cores, a particularly preferable form is a tape yarn or a highly oriented monofilament containing PTFE in view of chemical resistance and heat resistance. Specifically, a high-strength porous sheet made of PTFE is a tape yarn slitted in tape form, or a 50 to 300 denier of a highly oriented monofilament made of PTFE, and a woven density of 10 to 50 lines / inch. It is more preferable that it is a reinforcement core material whose thickness is the range of 50-100 micrometers. It is more preferable that the opening ratio of the ion exchange membrane including such a reinforcing core material is 60% or more.

Examples of the shape of the reinforcing yarn include round yarns and tape-like yarns.

(Communication hole)

It is preferable that the ion exchange membrane has a communication hole inside the membrane main body.

The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, a communication hole is a tubular hole formed in the inside of a membrane main body, and is formed by eluting the sacrificial core material (or sacrificial thread) mentioned later. The shape and diameter of the communication hole can be controlled by selecting the shape and diameter of the sacrificial core material (sacrificial yarn).

By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured at the time of electrolysis. Although the shape of a communication hole is not specifically limited, According to the manufacturing method mentioned later, it can be set as the shape of the sacrificial core material used for formation of a communication hole.

The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With such a structure, in the part where the communication hole is formed in the cathode side of the reinforcing core material, ions (for example, sodium ions) transported through the electrolyte solution filled in the communication hole can also flow to the cathode side of the reinforcing core material. As a result, since the flow of cation is not blocked, the electrical resistance of the ion exchange membrane can be made lower.

The communication hole may be formed along only one predetermined direction of the membrane main body constituting the ion exchange membrane, but is formed in both the longitudinal direction and the transverse direction of the membrane main body in view of exhibiting more stable electrolytic performance. desirable.

[Production method]

As a suitable manufacturing method of an ion exchange membrane, the method of having the following (1) process-(6) process is mentioned.

(1) Process: The process of manufacturing the fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(2) Process: If necessary, a sacrificial yarn is disposed between adjacent reinforcing cores by at least weaving a plurality of reinforcing cores and a property of dissolving in an acid or alkali and forming at least a communication hole. To obtain the finished reinforcement.

(3) Process: The process of film-forming the said fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(4) Step: The step of embedding the reinforcing material in the film as necessary to obtain a membrane body having the reinforcing material disposed therein.

(5) Process: The process (hydrolysis process) of hydrolyzing the membrane main body obtained at process (4).

(6) Process: The process (coating process) of forming a coating layer in the film main body obtained at the process (5).

Hereinafter, each process is explained in full detail.

(1) Process: process for producing fluorine-containing polymer

In the step (1), the fluorine-containing polymer is produced by using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of a fluorine-containing polymer, in the manufacture of the fluorine-containing polymer which forms each layer, the mixing ratio of the monomer of a raw material may be adjusted.

(2) Process: manufacturing process of reinforcement

A reinforcing material is a woven fabric etc. which woven the reinforcement yarn. The reinforcing material is embedded in the film to form the reinforcing core material. When using an ion exchange membrane having communication holes, the sacrificial yarn is also woven into the reinforcing material. In this case, the blending amount of the sacrificial material is preferably 10 to 80 mass%, more preferably 30 to 70 mass% of the entire reinforcing material. By weaving a sacrificial thread, the mesh shift | offset of a reinforcement core material can also be prevented.

The sacrificial material has solubility in a film production process or an electrolytic environment, and rayon, polyethylene terephthalate (PET), cellulose, polyamide, and the like are used. Moreover, polyvinyl alcohol etc. which have a thickness of 20-50 denier and consist of monofilament or multifilament are also preferable.

In the step (2), by adjusting the arrangement of the reinforcing core material or the sacrificial material, the opening ratio, the arrangement of the communication holes, and the like can be controlled.

(3) process: filming process

In the step (3), the fluorine-containing polymer obtained in the step (1) is filmed using an extruder. A single layer structure may be sufficient as a film, and as above-mentioned, the two-layered structure of a sulfonic acid layer and a carboxylic acid layer may be sufficient, and the multilayered structure of three or more layers may be sufficient as it.

As a method of film-forming, the following are mentioned, for example.

A method of filming each of the fluorine-containing polymer having a carboxylic acid group and the fluorine-containing polymer having a sulfonic acid group separately.

A method in which a fluorine-containing polymer having a carboxylic acid group and a fluorine-containing polymer having a sulfonic acid group are co-extruded into a composite film.

In addition, a plurality of films may be sufficient respectively. Moreover, coextrusion of different kinds of films is preferable because it contributes to raising the adhesive strength of an interface.

(4) step: the step of obtaining the membrane body

In the step (4), the film body in which the reinforcing material is embedded is obtained by embedding the reinforcing material obtained in the step (2) inside the film obtained in the step (3).

As a preferable formation method of a film main body, (i) the fluorine-containing polymer which has a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) located in the cathode side (henceforth, the layer which consists of this is called a 1st layer), And forming a fluorine-containing polymer having a sulfonic acid group precursor (e.g., a sulfonylfluoride functional group) (hereinafter, referred to as a second layer) by a coextrusion method, and heating and vacuum source as necessary. Is laminated on a flat plate or drum having a large number of pores on the surface of the reinforcing material and the second layer / first layer composite film in the order of a reinforcing material and a heat-resistant release paper having air permeability. Integrating while removing air between each layer by decompression under temperature; (ii) Apart from the second layer / first layer composite film, the fluorine-containing polymer (third layer) having a sulfonic acid group precursor is previously filmed alone, and the surface is heated and heated using a vacuum source if necessary. The laminated film was laminated in the order of a composite film consisting of a third layer film, a reinforcing core material, and a second layer / first layer via a heat-resistant release paper having air permeability on a flat plate or a drum having a large number of pores thereon. The method of integrating, removing the air between each layer by pressure reduction under the temperature which melt | dissolves is mentioned.

Here, coextrusion of a 1st layer and a 2nd layer contributes to raising the adhesive strength of an interface.

Moreover, the method of integrating under reduced pressure has the feature that the thickness of the 3rd layer on a reinforcement material becomes large compared with the pressure press method. In addition, since the reinforcing material is fixed to the inner surface of the membrane main body, it has the performance of sufficiently maintaining the mechanical strength of the ion exchange membrane.

In addition, the variation of lamination described here is an example, and considering the desired layer structure, physical properties, etc. of a film body, a suitable lamination pattern (for example, the combination of each layer, etc.) can be selected, and then co-extruded.

Further, in order to further improve the electrical performance of the ion exchange membrane, a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is further interposed between the first layer and the second layer. It is also possible to use a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor instead of the layer.

The method for forming the fourth layer may be a method of separately preparing a fluorine-containing polymer having a carboxylic acid group precursor and a fluorine-containing polymer having a sulfonic acid group precursor, and then mixing the monomers with the carboxylic acid group precursor and the sulfonic acid group precursor. The method of copolymerizing the monomer which has the thing may be used.

In the case where the fourth layer is configured as an ion exchange membrane, the coextruded film of the first layer and the fourth layer is molded, and the third layer and the second layer are filmed independently of this, by the method described above. You may laminate | stack and three layers of a 1st layer / 4th layer / 2nd layer may be film-formed by coextrusion at once.

In this case, the direction in which the extruded film flows is the MD direction. In this way, a membrane body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material.

In addition, the ion exchange membrane preferably has a protruding portion, that is, a convex portion, made of a fluorine-containing polymer having a sulfonic acid group, on the surface side of the sulfonic acid layer. It does not specifically limit as a method of forming such a convex part, The well-known method of forming a convex part in the resin surface can be employ | adopted. Specifically, the method of embossing on the surface of a film main body is mentioned, for example. For example, when the said composite film, reinforcing material, etc. are integrated, the said convex part can be formed by using the release paper previously embossed. When forming a convex part by embossing, control of the height and placement density of a convex part can be performed by controlling the emboss shape (shape of a release paper) to be transferred.

(5) hydrolysis process

In the step (5), the membrane body obtained in the step (4) is hydrolyzed to convert the ion exchanger precursor into the ion exchanger (hydrolysis step).

In the step (5), the elution hole can be formed in the membrane main body by dissolving and removing the sacrificial yarn contained in the membrane main body with an acid or an alkali. In addition, the sacrificial yarn may remain in the communication hole without being completely dissolved and removed. In addition, the sacrificial yarn remaining in the communication hole may be dissolved and removed by the electrolytic solution when the ion exchange membrane is provided for electrolysis.

The sacrificial yarn is soluble in acid or alkali in the ion exchange membrane production process or in an electrolytic environment, and communication holes are formed in the site by dissolving the sacrificial material.

The step (5) can be performed by immersing the membrane body obtained in the step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (dimethyl sulfoxide) can be used.

The said mixed solution contains 2.5-4.0 N of KOH, and 25-35 mass% of DMSO

 It is preferable to include.

As temperature of hydrolysis, it is preferable that it is 70-100 degreeC. The higher the temperature, the thicker the apparent thickness. More preferably, it is 75-100 degreeC.

It is preferable that it is 10 to 120 minutes as time of hydrolysis. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes.

Here, the process of forming a communication hole by eluting a sacrificial yarn is demonstrated in detail. 99 (a) and 99 (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane.

99 (a) and 99 (b), only the communication hole 504 formed by the reinforcement yarn 52, the sacrificial yarn 504a, and the sacrificial yarn 504a is shown. The illustration is omitted.

First, the reinforcement yarn 52 which comprises a reinforcing core material in an ion exchange membrane, and the sacrificial yarn 504a for forming the communication hole 504 in an ion exchange membrane are used as a knitted reinforcement material. And the communication hole 504 is formed by eluting the sacrificial yarn 504a in the process (5).

According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a may be adjusted in accordance with the arrangement of the reinforcing core and the communication hole in the membrane main body of the ion exchange membrane.

In FIG. 99 (a), although the reinforcement of the plain weave which woven the reinforcement yarn 52 and the sacrificial yarn 504a in both the longitudinal direction and the horizontal direction in the ground is illustrated, the reinforcement yarn in a reinforcement material as needed. The arrangement of the 52 and the victim 504a can be changed.

(6) coating process

In the step (6), the coating layer can be formed by preparing a coating liquid containing the inorganic particles obtained by gemstone grinding or melting of the gemstone and a binder, and applying and drying the coating liquid on the surface of the ion exchange membrane obtained in the step (5). .

As a binder, after hydrolyzing the fluorine-containing polymer having an ion exchange group precursor with an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH), it is immersed in hydrochloric acid to replace the counter ion of the ion exchange group with H ⁺ . One binder (eg, a fluorine-containing polymer having a carboxyl or sulfo group) is preferred. Since it becomes easy to melt | dissolve in water and ethanol mentioned later by this, it is preferable.

This binder is dissolved in a solution in which water and ethanol are mixed. Moreover, the preferable volume ratio of water and ethanol is 10: 1-1:10, More preferably, it is 5: 1-1: 5, More preferably, it is 2: 1-1: 2. In the solution thus obtained, the inorganic particles are dispersed by a ball mill to obtain a coating solution. At this time, the average particle diameter of a particle | grains, etc. can also be adjusted by adjusting the time and the rotation speed at the time of dispersion. In addition, the preferable compounding quantity of an inorganic particle and a binder is as above-mentioned.

The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, but is preferably a light coating liquid. Thereby, it becomes possible to apply | coat uniformly to the surface of an ion exchange membrane.

In addition, when dispersing the inorganic particles, a surfactant may be added to the dispersion. As surfactant, a nonionic surfactant is preferable, For example, HS-210, NS-210, P-210, E-212 by Nichi-yu Corporation, etc. are mentioned.

An ion exchange membrane is obtained by apply | coating the obtained coating liquid to the surface of an ion exchange membrane by spray coating or roll coating.

[Microporous membrane]

As described above, the microporous membrane of the present embodiment is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various microporous membranes can be applied.

Although the porosity of the microporous membrane of this embodiment is not specifically limited, For example, it can be 20-90, Preferably it is 30-85. The porosity can be calculated by the following formula, for example.

Porosity = (1- (Dry Film Weight in Dry State) / (Volume calculated from the thickness, width and length of the film and weight calculated from the density of the film material)) × 100

Although the average pore diameter of the microporous membrane of this embodiment is not specifically limited, For example, it can be 0.01 micrometer-10 micrometers, Preferably it is 0.05 micrometer-5 micrometers. The average pore diameter is, for example, the film is vertically cut in the thickness direction, and the cut surface is observed by FE-SEM. It can obtain | require by measuring and averaging about 100 points of the diameter of the hole observed.

Although the thickness of the microporous film of this embodiment is not specifically limited, For example, it can be 10 micrometers-1000 micrometers, Preferably it is 50 micrometers-600 micrometers. The said thickness can be measured using a micrometer (made by Mitsutoyo Corporation) etc., for example.

Specific examples of the microporous membranes described above include Agir's Zirfon Perl UTP 500 (also referred to as Zirfon membrane in this embodiment), International Publication No. 2013-183584, International Publication No. 2016-203701, etc. The things described are mentioned.

In this embodiment, it is preferable that a diaphragm contains the 1st ion exchange resin layer and the 2nd ion exchange resin layer which has EW (ion exchange equivalent) different from this 1st ion exchange resin layer. Moreover, it is preferable that a diaphragm contains the 1st ion exchange resin layer and the 2nd ion exchange resin layer which has a functional group different from this 1st ion exchange resin layer. An ion exchange equivalent can be adjusted with the functional group to introduce | transduce, and the functional group which can be introduce | transduced is as above-mentioned.

(Hydraulic)

As the electrolytic cell in this embodiment, the electrolytic cell in the case of performing electrolysis has a structure which changed the ion exchange membrane in the electrolytic cell in the case of performing the above-mentioned salt electrolysis to a microporous membrane. In addition, since the raw material to be supplied is water, it differs from the electrolytic cell in the case of performing the above-mentioned salt electrolysis. As for other configurations, the same configuration as the electrolytic cell in the case of performing salt electrolysis can also be adopted. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. However, in the case of hydrolysis, since oxygen gas is only generated in the anode chamber, the same material as the cathode chamber is used. Can be used. For example, nickel etc. can be mentioned. In addition, the anode coating is suitably a catalyst coating for oxygen generation. Examples of catalyst coatings include metals, oxides, hydroxides, and the like of platinum group metals and transition metals. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used.

[Update of Electrode]

The manufacturing method of the electrolytic cell which concerns on this embodiment can be implemented also as a updating method of an electrode (anode and / or a cathode). That is, the update method of the electrode which concerns on this embodiment is a method for updating an existing electrode by using an electrode for electrolysis, and uses the winding body of the said electrode for electrolysis.

Although not limited to the following as a specific example of the process of using a winding body, the method etc. which arrange | position the thing which canceled the wound state of the winding body of an electrode for electrolysis are mentioned. By this method, the electrolytic electrode can be disposed on the surface of the existing anode or cathode, and the performance of the anode and / or cathode can be updated.

As mentioned above, it is preferable that the process of using a wound body in this embodiment has a process (B ') of releasing the wound state of a wound body, and after a process (B'), it is on the surface of an existing electrode. It is more preferable to have a process (C ') which arrange | positions an electrode for electrolysis.

Moreover, in the electrode update method which concerns on this embodiment, it is preferable that the process of using a wound body has the process (A ') of holding the electrode for electrolysis in a wound state, and obtaining a wound body. In process (A '), the electrolytic electrode itself may be wound up to be a wound body, or the electrolytic electrode may be wound up to a core to form a wound body. Although it does not specifically limit as a core which can be used here, For example, it has a substantially cylindrical shape, and can use the member of the size according to the electrode for electrolysis.

[Manufacturing method of winding object]

In the manufacturing method of the electrolytic cell which concerns on this embodiment, and the update method of the electrode which concerns on this embodiment, the process (A) or (A ') which can be performed can also be performed as a manufacturing method of a winding object. That is, the manufacturing method of the winding body which concerns on this embodiment is a manufacturing method of the winding body for updating the existing electrolytic cell provided with a positive electrode, the negative electrode which opposes the said positive electrode, and the diaphragm arrange | positioned between the positive electrode and the said negative electrode. And winding the laminate of the electrolytic electrode or the electrolytic electrode and the new diaphragm to obtain the wound body. In the process of obtaining a wound body, the electrolytic electrode itself may be wound into a wound body, or the electrolytic electrode may be wound around a core to form a wound body. Although it does not specifically limit as a core which can be used here, For example, it has a substantially cylindrical shape, and can use the member of the size according to the electrode for electrolysis.

Sixth Embodiment

Here, the 6th Embodiment of this invention is described in detail, referring FIGS. 103-111.

[Method of Manufacturing Electrolyzer]

A method for producing an electrolytic cell according to a sixth embodiment (hereinafter simply referred to as "the present embodiment" in the section of <Sixth Embodiment>) includes an anode, a cathode facing the anode, and between the anode and the cathode. A method for producing a new electrolytic cell by disposing a laminate in an existing electrolytic cell having a diaphragm disposed in the above, wherein the laminate is integrated by integrating an electrode for electrolysis and a new diaphragm under a temperature at which the diaphragm does not melt. It has a process (A) of obtaining and the process (B) of exchanging the said diaphragm in an existing electrolytic cell with the said laminated body after the said process (A).

As mentioned above, according to the manufacturing method of the electrolytic cell which concerns on this embodiment, since the electrode for electrolysis and a diaphragm can be used integrally, without using a non-practical method like thermocompression bonding, the work efficiency at the time of electrode update in an electrolytic cell is used. Can improve.

In the present embodiment, the existing electrolytic cell includes a positive electrode, a negative electrode facing the positive electrode, and a diaphragm disposed between the positive electrode and the negative electrode as a constituent member, in other words, an electrolytic cell. The existing electrolytic cell is not specifically limited as long as it contains the said structural member, Various well-known structures can be applied.

In the present embodiment, the new electrolytic cell further includes an electrode for electrolysis or a laminate in addition to a member that already functions as an anode or a cathode in the existing electrolytic cell. That is, the "electrode for electrolysis" arrange | positioned at the time of manufacture of a new electrolytic cell functions as an anode or a cathode, and is separate from the cathode and anode in an existing electrolytic cell. In the present embodiment, even when the electrolytic performance of the positive electrode and / or the negative electrode deteriorates due to the operation of the existing electrolytic cell, the performance of the positive electrode and / or the negative electrode can be updated by disposing the electrode for electrolysis separate from these. Moreover, since the new ion exchange membrane which comprises a laminated body is also arrange | positioned together, the performance of the ion exchange membrane whose performance deteriorated with operation can also be updated simultaneously. The term "update performance" as used herein means that the performance is equal to the initial performance which the existing electrolytic cell had before being provided for operation, or the performance is higher than the initial performance.

In this embodiment, the existing electrolytic cell assumes "electrolyte already provided for operation", and the new electrolytic cell assumes "electrolyte not provided for operation yet". That is, once the electrolytic cell manufactured as a new electrolytic cell is provided to operation, it becomes "the existing electrolytic cell in this embodiment", and it is "the new electrolytic cell in this embodiment" which arrange | positioned the electrode or laminated body for this existing electrolytic cell. Becomes

EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of an electrolytic cell is explained in full detail, for example, when salt electrolysis is performed using an ion exchange membrane as a diaphragm. In addition, "electrolyzer in this embodiment" includes both "existing electrolyzer in this embodiment" and "new electrolyzer in this embodiment", unless specifically mentioned in the term of <6th embodiment>. will be.

[Electrolysis cell]

First, the electrolytic cell which can be used as a structural unit of the electrolytic cell in this embodiment is demonstrated. 103 is a cross-sectional view of the electrolytic cell 1.

The electrolytic cell 1 includes the anode chamber 10, the cathode chamber 20, the partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, and the anode provided in the anode chamber 10. 11 and a cathode 21 provided in the cathode chamber 20. If necessary, the base 18a and the reverse current absorbing layer 18b formed on the base 18a may be provided, and the reverse current absorber 18 provided in the cathode chamber may be provided. The positive electrode 11 and the negative electrode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 has the following cathode structure. The negative electrode structure 40 includes a negative electrode chamber 20, a negative electrode 21 provided in the negative electrode chamber 20, and a reverse current absorber 18 provided in the negative electrode chamber 20, and the reverse current absorber 18. 107 has the base material 18a and the reverse current absorption layer 18b formed on this base material 18a, and the cathode 21 and the reverse current absorption layer 18b are electrically connected. The negative electrode chamber 20 further includes a current collector 23, a support 24 supporting the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the electrical power collector 23 and the negative electrode 21. The support body 24 is provided between the collector 23 and the partition 30. The current collector 23 is electrically connected to the negative electrode 21 via the metal elastic body 22. The partition 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition 30, the support body 24, the collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected to each other. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be connected indirectly via a current collector, a support, a metal elastic body, a partition, or the like. It is preferable that the whole surface of the cathode 21 is covered with a catalyst layer for the reduction reaction. In addition, in the form of electrical connection, the partition 30 and the support body 24, the support body 24 and the collector 23, the collector 23 and the metal elastic body 22 are respectively directly attached, and the metal elastic body 22 ) May be laminated on the cathode 21. Welding etc. are mentioned as a method of attaching these structural members directly to each other. In addition, the reverse current absorber 18, the negative electrode 21, and the current collector 23 may be collectively referred to as the negative electrode structure 40.

FIG. 104 is a cross-sectional view of two electrolytic cells 1 adjacent in the electrolytic cell 4. 105 shows the electrolytic cell 4. 106 shows a step of assembling the electrolytic cell 4.

As shown in FIG. 104, the electrolytic cell 1, the cation exchange membrane 2, and the electrolytic cell 1 are arranged in series in this order. The ion exchange membrane 2 is arrange | positioned between the anode chamber of one electrolytic cell 1 and the cathode chamber of the other electrolytic cell 1 among two electrolytic cells which adjoin in an electrolytic cell. In other words, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are spaced apart by the cation exchange membrane 2. As shown in FIG. 105, the electrolytic cell 4 is composed of a plurality of electrolytic cells 1 connected in series via an ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer having a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 106, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series via an ion exchange membrane 2, and being connected by a press 5.

The electrolytic cell 4 has the positive terminal 7 and the negative terminal 6 connected to a power supply. The positive electrode 11 of the electrolytic cell 1 positioned at the shortest of the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4 is electrically connected to the positive electrode terminal 7. Among the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4, the negative electrode 21 of the electrolytic cell located at the end opposite to the positive electrode terminal 7 is electrically connected to the negative electrode terminal 6. The electric current at the time of electrolysis flows toward the negative electrode terminal 6 from the positive terminal 7 side via the positive electrode and the negative electrode of each electrolytic cell 1. Moreover, you may arrange | position the electrolytic cell (anode terminal cell) which has only an anode chamber, and the electrolytic cell (cathode terminal cell) which has only a cathode chamber in the both ends of the electrolytic cell 1 which connected. In this case, the positive terminal 7 is connected to the positive terminal cell disposed at one end thereof, and the negative terminal 6 is connected to the negative terminal cell arranged at the other end thereof.

In the case of electrolysis of brine, brine is supplied to each anode chamber 10, and pure or low concentration aqueous sodium hydroxide solution is supplied to the cathode chamber 20. Each liquid is supplied to each electrolytic cell 1 from electrolyte supply pipe (not shown) via electrolyte supply hose (not shown). In addition, electrolyte solution and the product by electrolysis are collect | recovered from an electrolyte collection pipe (not shown). In electrolysis, sodium ions in brine move from the anode chamber 10 of one electrolytic cell 1 through the ion exchange membrane 2 to the cathode chamber 20 of the neighboring electrolytic cell 1. Therefore, the current during electrolysis flows along the direction in which the electrolytic cells 1 are connected in series. That is, the current flows from the anode chamber 10 toward the cathode chamber 20 via the cation exchange membrane 2. By electrolysis of the brine, chlorine gas is produced on the anode 11 side, and sodium hydroxide (solute) and hydrogen gas are produced on the cathode 21 side.

(Positive room)

The anode chamber 10 includes a cathode 11 or an anode feeder 11. The term "feeder" as used herein means a deteriorated electrode (that is, an existing electrode), an electrode not coated with a catalyst, or the like. When the electrode for electrolysis in this embodiment is inserted in the anode side, 11 functions as a positive electrode feeder. When the electrode for electrolysis in this embodiment is not inserted in the anode side, 11 functions as an anode. In addition, the anode chamber 10 is disposed on an anode side electrolyte supply portion for supplying an electrolyte solution to the anode chamber 10 and an anode side electrolyte supply portion, and a baffle plate disposed to be substantially parallel or oblique with the partition wall 30. And it is preferable to have an anode side gas-liquid separation part arrange | positioned above the baffle plate and isolate | separates a gas from the electrolyte solution which gas mixed.

(anode)

When the electrode for electrolysis in this embodiment is not inserted in the anode side, the anode 11 is provided in the frame (namely, anode frame) of the anode chamber 10. As the anode 11, a metal electrode such as so-called DSA (registered trademark) can be used. DSA is a titanium-based electrode whose surface was covered with an oxide containing ruthenium, iridium and titanium.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Positive electrode feeder)

When the electrode for electrolysis in this embodiment is inserted in the anode side, the positive electrode feeder 11 is provided in the frame of the anode chamber 10. As the positive electrode feeder 11, a metal electrode such as DSA (registered trademark) or the like may be used, or titanium without a catalyst coating may be used. It is also possible to use DSA with a thinner catalyst coating thickness. Moreover, the used anode can also be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Anode-side electrolyte supply unit)

The anode-side electrolyte supply unit supplies the electrolyte solution to the anode chamber 10 and is connected to the electrolyte solution supply pipe. It is preferable that an anode side electrolyte supply part is arrange | positioned under the anode chamber 10. As an anode side electrolyte supply part, the pipe (dispersion pipe) etc. which have an opening part formed in the surface can be used, for example. It is more preferable that such a pipe is arrange | positioned in parallel with the bottom part 19 of an electrolysis cell along the surface of the anode 11. This pipe is connected to the electrolyte supply pipe (liquid supply nozzle) which supplies electrolyte solution in the electrolysis cell 1. The electrolyte solution supplied from the liquid supply nozzle is conveyed to the electrolysis cell 1 by the pipe, and is supplied to the inside of the anode chamber 10 from the opening provided in the surface of the pipe. By arranging the pipes parallel to the bottom portion 19 of the electrolytic cell along the surface of the anode 11, the electrolyte can be uniformly supplied into the anode chamber 10, which is preferable.

(Positive side gas-liquid separator)

It is preferable that the anode-side gas-liquid separator is disposed above the baffle plate. During electrolysis, the anode-side gas-liquid separator has a function of separating the generated gas such as chlorine gas and the electrolyte. In addition, unless otherwise indicated, an upper side means the upward direction in the electrolysis cell 1 of FIG. 103, and a lower side means the downward direction in the electrolysis cell 1 of FIG.

At the time of electrolysis, when the generated gas and electrolyte generated in the electrolytic cell 1 become mixed phase (gas-liquid mixed phase) and discharged out of the system, vibration occurs due to pressure fluctuation inside the electrolytic cell 1, and physical damage of the ion exchange membrane is prevented. I may cause it. In order to suppress this, it is preferable that the positive electrode side gas-liquid separation part for separating a gas and a liquid is provided in the electrolysis cell 1 of this embodiment. It is preferable that a defoaming plate for removing bubbles is provided in the anode-side gas-liquid separator. When a gas-liquid mixture flows through a vesicle plate, a bubble bursts and can be isolate | separated into electrolyte solution and gas. As a result, vibration during electrolysis can be prevented.

(Baffle version)

It is preferable that the baffle plate is disposed above the anode-side electrolyte supply portion, and is disposed substantially parallel to or inclined with the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. By providing the baffle plate, the electrolyte solution (salt water, etc.) can be circulated internally in the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged to be spaced apart from the space near the anode 11 and the space near the partition wall 30. From this viewpoint, the baffle plate is preferably provided so as to face each surface of the anode 11 and the partition wall 30. In the space near the anode partitioned by the baffle plate, electrolytic solution concentration (saline concentration) decreases as electrolysis proceeds, and product gas such as chlorine gas is generated. Thereby, the specific gravity difference of gas-liquid arises in the space near the anode 11 divided by the baffle plate, and the space near the partition 30. As shown in FIG. By using this, the internal circulation of the electrolyte solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolyte solution in the anode chamber 10 can be made more uniform.

Although not shown in FIG. 103, a current collector may be separately provided inside the positive electrode chamber 10. As such an electrical power collector, it can also be set as the material and structure similar to the electrical power collector of the negative electrode chamber mentioned later. In the anode chamber 10, the anode 11 itself can also function as a current collector.

(septum)

The partition 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition 30 may be called a separator and divides the anode chamber 10 and the cathode chamber 20. As the partition 30, a well-known thing can be used as a separator for electrolysis, For example, the partition which welded the plate which consists of nickel to the cathode side, and titanium to the anode side, etc. are mentioned.

(Cathode room)

The cathode chamber 20 functions as a cathode feeder when the electrode for electrolysis in the present embodiment is inserted on the cathode side, and when the electrode for electrolyte in the present embodiment is not inserted on the cathode side. , 21 functions as a cathode. When the reverse current absorber is provided, the negative electrode or the negative electrode feeder 21 and the reverse current absorber are electrically connected to each other. In addition, it is preferable that the cathode chamber 20 also has a cathode side electrolyte solution supply section and a cathode side gas-liquid separation section similarly to the anode chamber 10. In addition, description is abbreviate | omitted about the same thing as each part which comprises the anode chamber 10 among each site | part which comprises the cathode chamber 20. As shown in FIG.

(cathode)

When the electrode for electrolysis in this embodiment is not inserted in the cathode side, the cathode 21 is provided in the frame (namely, the cathode frame) of the cathode chamber 20. It is preferable that the negative electrode 21 has a catalyst layer which covers a nickel substrate and a nickel substrate. As a component of the catalyst layer on the nickel substrate, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd , Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho And metals such as Er, Tm, Yb and Lu, and oxides or hydroxides of the metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may give reduction process to the negative electrode 21 as needed. As the base material of the negative electrode 21, one in which nickel, nickel alloy, iron, or stainless steel is plated with nickel may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Cathode feeder)

When the electrode for electrolysis in this embodiment is inserted in the cathode side, the negative electrode feeder 21 is provided in the frame of the cathode chamber 20. The catalyst component may be coated on the negative electrode feeder 21. The catalyst component may be originally used as a negative electrode and remain. As components of the catalyst layer, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Metals, such as Tm, Yb, Lu, and the oxide or hydroxide of this metal are mentioned. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may use what plated nickel with nickel, nickel alloys, iron, or stainless steel which are not catalyst coated. As the base material of the negative electrode feeder 21, a plated nickel on nickel, a nickel alloy, iron or stainless may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

Reverse Current Absorption Layer

A material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected as the material of the reverse current absorbing layer. For example, nickel, iron, etc. are mentioned.

(Current collector)

The negative electrode chamber 20 preferably includes a current collector 23. This increases the current collecting effect. In the present embodiment, the current collector 23 is a porous plate, and is preferably disposed substantially parallel to the surface of the negative electrode 21.

The current collector 23 is preferably made of an electrically conductive metal such as nickel, iron, copper, silver, titanium, or the like. The current collector 23 may be a mixture of these metals, an alloy or a composite oxide. In addition, as long as it is a shape which functions as an electrical power collector, the shape of the electrical power collector 23 may be any shape, and plate-shaped or network-shaped may be sufficient as it.

(Metal elastomer)

By providing the metal elastic body 22 between the collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, The distance between each anode 11 and each cathode 21 can be shortened, and the voltage applied to the entire plurality of electrolytic cells 1 connected in series can be lowered. By lowering the voltage, the total consumption can be reduced. Moreover, when the metal elastic body 22 is provided and the laminated body containing the electrode for electrolysis in this embodiment is installed in an electrolytic cell, the said electrode for electrolysis by the pressure pressed by the metal elastic body 22 is carried out. Can be kept in a stable position.

As the metallic elastic body 22, a spring member, such as a spiral spring and a coil, a cushion mat, etc. can be used. As the metal elastic body 22, a suitable one can be appropriately adopted in consideration of a stress or the like which presses the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the collector 23 on the cathode chamber 20 side, or may be provided on the surface of the partition wall on the anode chamber 10 side. Usually, since both chambers are partitioned so that the cathode chamber 20 becomes smaller than the anode chamber 10, from the viewpoint of the strength of the frame or the like, the metal elastic body 22 is used for the current collector 23 of the cathode chamber 20. It is preferable to provide between and the cathode 21. Moreover, it is preferable that the metal elastic body 22 consists of metal which has electrical conductivity, such as nickel, iron, copper, silver, titanium.

(Support)

The negative electrode chamber 20 preferably includes a support 24 for electrically connecting the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently.

The support 24 is preferably made of a metal having electrical conductivity such as nickel, iron, copper, silver, titanium, or the like. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod, plate, or network. The support body 24 is plate-shaped, for example. The plurality of supports 24 are disposed between the partition wall 30 and the current collector 23. The plurality of supports 24 are arranged such that their respective surfaces are parallel to each other. The support body 24 is disposed substantially perpendicular to the partition wall 30 and the current collector 23.

(Anode side gasket, cathode side gasket)

It is preferable that the anode side gasket is arranged on the surface of the frame body constituting the anode chamber 10. It is preferable that the cathode side gasket is arrange | positioned at the surface of the frame body which comprises the cathode chamber 20. As shown in FIG. The anode side gasket of one electrolytic cell and the cathode side gasket of the electrolytic cell adjacent to this are connected so that the electrolytic cells may be clamped by the ion exchange membrane 2 (refer FIG. 104). By these gaskets, when connecting a plurality of electrolytic cells 1 in series via the ion exchange membrane 2, airtightness can be provided to a connection location.

A gasket seals between an ion exchange membrane and an electrolysis cell. As a specific example of a gasket, a frame-shaped rubber sheet etc. in which the opening part was formed in the center are mentioned. The gasket is required to be resistant to corrosive electrolytes, generated gases and the like and to be used for a long time. Therefore, from the viewpoint of chemical resistance and hardness, vulcanized products, peroxide crosslinked products and the like of ethylene propylene diene rubber (EPDM rubber) and ethylene propylene rubber (EPM rubber) are usually used as the gasket. Moreover, the gasket which coat | covered the area | region (contact part) which contact | connects a liquid as needed with fluororesin, such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether polymer (PFA), can also be used. These gaskets should just have opening parts, respectively, so that the flow of electrolyte solution may not be disturbed, The shape is not specifically limited. For example, a frame-shaped gasket is bonded with an adhesive or the like along the circumferential edge of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20. For example, when connecting two electrolytic cells 1 via the ion exchange membrane 2 (refer FIG. 104), when each electrolytic cell 1 which bonded the gasket through the ion exchange membrane 2 is fastened, do. Thereby, it can suppress that an electrolyte solution, the alkali metal hydroxide produced by electrolysis, chlorine gas, hydrogen gas, etc. leak to the exterior of the electrolysis cell 1.

[Laminated body]

The electrode for electrolysis in this embodiment is used as a laminated body with septum, such as an ion exchange membrane and a microporous membrane. That is, the laminated body in this embodiment contains an electrode for electrolysis and a new diaphragm. The new diaphragm is not particularly limited as long as it is separate from the diaphragm in the existing electrolytic cell, and various known diaphragms can be applied. The new diaphragm may be the same as the diaphragm in the existing electrolytic cell in terms of material, shape, physical properties, and the like. Specific examples of the electrode for electrolysis and the diaphragm will be described later in detail.

(Step (A))

In the process (A) in this embodiment, a laminated body is obtained by integrating an electrode for electrolysis and a new diaphragm under the temperature which the said diaphragm does not melt.

"The temperature at which a diaphragm does not melt" can be specified as a softening point of a new diaphragm. Although the said temperature can vary with the material which comprises a diaphragm, it is preferable that it is 0-100 degreeC, It is more preferable that it is 5-80 degreeC, It is still more preferable that it is 10-50 degreeC.

In addition, it is preferable that the said integration is performed under normal pressure.

As a specific method of the said integration, all the methods except the typical method of melting a diaphragm, such as thermocompression bonding, can be used, It does not specifically limit. As a preferable example, the method etc. which integrate with the surface tension of the said liquid through the liquid between the electrolytic electrode mentioned later and a diaphragm are mentioned.

[Step (B)]

In process (B) in this embodiment, after process (A), the diaphragm in an existing electrolytic cell is exchanged with a laminated body. The method of exchange is not particularly limited, but for example, first, in an existing electrolytic cell, the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine is released, and a gap is formed between the electrolytic cell and the ion exchange membrane. The method of removing the existing ion exchange membrane used as an update object, inserting a laminated body into the said space | gap, and then connecting each member by the press machine, etc. are mentioned. By this method, the laminate can be disposed on the surface of the anode or cathode in the existing electrolytic cell, and the performance of the ion exchange membrane, the anode and / or the cathode can be updated.

[Electrode Electrode]

In the present embodiment, the electrode for electrolysis is not particularly limited as long as it can be integrated with a new diaphragm as described above, that is, it can be integrated. The electrode for electrolysis may function as a cathode in an electrolytic cell, or may function as an anode. In addition, regarding the material, shape, etc. of the electrode for electrolysis, an appropriate thing can be selected suitably in consideration of the process (A), (B) in this embodiment, the structure of an electrolytic cell, etc. Hereinafter, although the preferable aspect of the electrode for electrolysis in this embodiment is demonstrated, these are only illustrations of the preferable aspect in integrating with a new diaphragm to the last, and electrolytic electrodes other than the aspect mentioned later can also be suitably employ | adopted. Can be.

The electrode for electrolysis in this embodiment can obtain favorable handling property, and is a unit from a viewpoint of having favorable adhesive force, such as a diaphragm, such as an ion exchange membrane and a microporous membrane, a feeder (a deteriorated electrode and a catalyst uncoated electrode), etc. The force applied per mass and unit area is preferably 1.6 N / (mg · cm 2) or less, more preferably less than 1.6 N / (mg · cm 2), still more preferably less than 1.5 N / (mg · cm 2) More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred.

From the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and even more preferably 0.1 N / mg · cm 2 or more. More preferably, it is 0.14 N / (mg * cm <2>) or more. 0.2 N / (mg * cm <2>) or more is more preferable from a viewpoint of the ease of handling in a large size (e.g., size 1.5 m x 2.5 m).

The said applied force can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, arithmetic mean surface roughness, etc., for example. More specifically, for example, when the porosity is increased, the applied force tends to be small, and when the porosity is decreased, the applied force tends to be large.

In addition, good handling properties can be obtained, good adhesion to diaphragms such as ion exchange membranes and microporous membranes, deteriorated electrodes, catalyst uncoated feeders and the like, and from the viewpoint of economy, the mass per unit area is 48 mg / cm 2 or less. It is preferable, More preferably, it is 30 mg / cm <2> or less, More preferably, it is 20 mg / cm <2> or less, It is preferable that it is 15 mg / cm <2> or less from a comprehensive viewpoint which combined handling property, adhesiveness, and economics. Although a lower limit is not specifically limited, For example, it is about 1 mg / cm <2>.

The said mass per unit area can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, etc., for example. More specifically, for example, if the thickness is the same, the mass per unit area tends to be smaller when the porosity is increased, and the mass per unit area tends to be larger when the porosity is reduced.

The force applied can be measured by the following method (i) or (ii) and is as having described in the Example in detail. The force applied is also referred to as the value obtained by the measurement of the method (i) (also referred to as "the applied force 1"), and the value obtained by the measurement of the method (ii) (also referred to as the "force 2 applied"). ) May be the same or different, but any value is preferably less than 1.5 N / mg · cm 2.

[Method (i)]

Nickel plate obtained by blasting with alumina of particle number 320 (thickness 1.2 mm, width 200 mm) and an ion exchange membrane coated with inorganic particles and a binder on both sides of a membrane of a perfluorocarbon polymer into which an ion exchanger was introduced (horizontal 170 mm in length and the details of the ion-exchange membrane here, as described in the Example) and an electrode sample (130 mm in length) were laminated in this order, and this laminated body was fully immersed in pure water, and then laminated body. A sample for measurement is obtained by removing excess moisture adhering to the surface. In addition, the arithmetic mean surface roughness Ra of the nickel plate after a blasting process is 0.5-0.8 micrometer. The specific calculation method of arithmetic mean surface roughness Ra is as having described in the Example.

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were raised in 10 mm in the vertical direction. Measure the weight when This measurement is performed three times to calculate an average value.

The average value is divided by the area of the overlapped portion of the electrode sample and the ion exchange membrane and the mass of the electrode sample of the overlapped portion with the ion exchange membrane, and the force applied per unit mass and unit area (1) (N / mg · cm 2) To calculate.

The force (1) applied per unit mass and unit area obtained by the method (i) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is preferable that it is 1.6 N / (mg * cm <2>) or less from a viewpoint of having more, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more and more preferably 0.14 N / (mg · cm 2) and 0.2 N / (mg · cm 2) from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m). ) Is more preferable.

[Method (ii)]

The nickel plate (thickness 1.2 mm, width 200 mm, the same nickel plate as the method (i)) and the electrode sample (length 130 mm) obtained by blasting with alumina of particle number 320 were laminated in this order. After fully immersing the laminate with pure water, a sample for measurement is obtained by removing excess moisture adhering to the laminate surface. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were 10 mm in the vertical direction. The weight at the time of rise is measured. This measurement is performed three times to calculate an average value.

This average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate, and the mass of the electrode sample in the overlapped portion of the nickel plate, and the adhesive force 2 per unit mass and unit area (N / mg · cm 2) is obtained. Calculate.

The force (2) applied per unit mass and unit area obtained by the method (ii) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is preferable that it is 1.6 N / (mg * cm <2>) or less from a viewpoint of having more, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more, and even more preferably, from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m), still more preferably 0.14 N / (mg · cm 2) or more.

It is preferable that the electrolytic electrode in this embodiment contains an electrolytic electrode base material and a catalyst layer. Although the thickness (gauge thickness) of the said electrolytic electrode base material is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feedstock), and an electrode without a catalyst coating (grade 300 micrometers or less are preferable from a viewpoint of having a good adhesive force with the whole), and being rolled suitably, being able to bend it favorably, and facilitating handling in a large size (e.g., size 1.5 m x 2.5 m). 205 micrometers or less are more preferable, 155 micrometers or less are more preferable, 135 micrometers or less are still more preferable, 125 micrometers or less are still more preferable, 120 micrometers or less are still more preferable, 100 micrometers or less are further more preferable In addition, from a viewpoint of handling property and economical efficiency, 50 micrometers or less are further more preferable. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In this embodiment, in integrating a new diaphragm and an electrode for electrolysis, it is preferable that a liquid is interposed between them. Any liquid may be used as long as the liquid generates surface tension such as water and an organic solvent. The greater the surface tension of the liquid, the greater the force exerted between the new diaphragm and the electrode for electrolysis. Therefore, a liquid having a large surface tension is preferable. Examples of the liquid include the following (the numerical values in parentheses indicate the surface tension at 20 ° C. of the liquid).

Hexane (20.44 mN / m), Acetone (23.30 mN / m), Methanol (24.00 mN / m), Ethanol (24.05 mN / m), Ethylene glycol (50.21 mN / m), Water (72.76 mN / m)

If the liquid has a large surface tension, the new diaphragm and the electrode for electrolysis are integrated (to form a laminate), and the electrode update tends to be easier. The liquid between the new diaphragm and the electrode for electrolysis needs only to be such that the amount of liquid adheres to each other by the surface tension, and as a result, the amount of liquid is small. Therefore, even if it is mixed in the electrolyte after installation in the electrolytic cell of the laminate, the electrolysis itself is affected. Does not have

From a practical point of view, it is preferable to use the liquid whose surface tension is 24 mN / m-80 mN / m, such as ethanol, ethylene glycol, water, as a liquid. In particular, an aqueous solution obtained by dissolving caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like in water or alkali is preferable. In addition, surfactants may be included in these liquids to adjust the surface tension. By including surfactant, the adhesiveness of a new diaphragm and an electrode for electrolysis changes, and handling property can be adjusted. It does not specifically limit as surfactant, Any one of an ionic surfactant and a nonionic surfactant can be used.

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), From the viewpoint of having good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and also in a large size (e.g., size 1.5 m x 2.5 m). It is more preferable that it is 95% or more from the viewpoint of easy handling. The upper limit is 100%.

[Method (2)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the condition of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 280 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), It is preferable that it is 75% or more, and it is more preferable that it is 80% or more from the viewpoint of having favorable adhesive force, and being able to wind up in roll shape suitably, and bend | bending favorably. It is more preferable that it is 90% or more from a viewpoint that handling at a size (for example, size 1.5 m x 2.5 m) becomes easy. The upper limit is 100%.

[Method (3)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 145 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), It is preferable that it has a favorable adhesive force and is a porous structure from a viewpoint of the prevention of the residence of the gas which arises during electrolysis, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80% or less, still more preferably 20 to 75%.

In addition, an opening ratio is a ratio of an opening part per unit volume. The calculation method varies depending on whether the opening is also considered to submicron order or only the visible opening. In this embodiment, the porosity A can be calculated by the following formula by calculating the volume V from the values of the gauge thickness, the width, and the length of the electrode, and by measuring the weight W.

A = (1- (W / (V × ρ)) × 100

ρ is the density (g / cm 3) of the material of the electrode. For example, 8.908 g / cm 3 for nickel and 4.506 g / cm 3 for titanium. The adjustment of the porosity is to change the area punching the metal per unit area if the punching metal, change the SW (short diameter), LW (long diameter), the feeding value if the expanded metal, the mesh diameter of the metal fiber, By changing the number of meshes, changing the pattern of the photoresist to be used for electroforming, changing the metal fiber diameter and fiber density for nonwoven fabrics, and changing the mold for forming the voids for the foamed metal, etc. I can adjust it.

Hereinafter, more specific embodiment of the electrode for electrolysis in this embodiment is demonstrated.

It is preferable that the electrolytic electrode which concerns on this embodiment contains an electrolytic electrode base material and a catalyst layer. The catalyst layer may be composed of a plurality of layers as described below or may have a single layer structure.

As illustrated in FIG. 108, the electrolytic electrode 100 according to the present embodiment includes a pair of first layers 20 covering both surfaces of the electrolytic electrode substrate 10 and the electrolytic electrode substrate 10. It is provided. It is preferable that the 1st layer 20 coat | covers the electrolytic electrode base material 10 whole. As a result, the catalytic activity and durability of the electrode for electrolysis tends to be improved. In addition, the first layer 20 may be laminated only on one surface of the electrode base 10 for electrolysis.

As shown in FIG. 108, the surface of the first layer 20 may be covered with the second layer 30. The second layer 30 preferably covers the entire first layer 20. In addition, only one surface of the first layer 20 may be laminated on the second layer 30.

(Electrode base for electrolysis)

The electrolytic electrode substrate 10 is not particularly limited, but a valve metal such as nickel, nickel alloy, stainless steel or titanium may be used, and at least one selected from nickel (Ni) and titanium (Ti) may be used. It is preferable to include the element of a species.

When stainless steel is used in a high concentration aqueous alkali solution, considering that iron and chromium are eluted, and that the electrical conductivity of stainless steel is about 1/10 of nickel, the electrolytic electrode substrate includes nickel (Ni). The substrate is preferred.

In addition, when the electrolytic electrode base material 10 is used in the chlorine gas generation | occurence atmosphere in the high concentration saline solution near saturation, it is preferable that a material is titanium with high corrosion resistance.

There is no restriction | limiting in particular in the shape of the electrode base material 10 for electrolysis, An appropriate shape can be selected according to the objective. As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used. Especially, a punching metal or an expanded metal is preferable. In addition, electroforming is a technique which manufactures a metal thin film of a precise pattern by combining photolithography and an electroplating method. It is a method of pattern-forming with a photoresist on a board | substrate, electroplating to the part which is not protected by a resist, and obtaining metal foil.

The shape of the electrode base material for electrolysis has suitable specifications depending on the distance between the anode and the cathode in the electrolytic cell. Although not particularly limited, in the case where the anode and the cathode have a finite distance, an expanded metal or a punched metal shape can be used, and in the case of a so-called zero gap electrolytic cell in which the ion exchange membrane and the electrode are in contact, a woven mesh woven with fine lines , Wire mesh, foamed metal, metal nonwoven fabric, expanded metal, punched metal, metal porous foil and the like can be used.

Examples of the electrode base 10 for electrolysis include a metal porous foil, a wire mesh, a metal nonwoven fabric, a punching metal, an expanded metal or a foamed metal.

As a board | plate material before processing with a punching metal and an expanded metal, the board | plate material roll-molded, electrolytic foil, etc. are preferable. It is preferable that the electrolytic foil is further plated with the same element as the base material as post-treatment to form irregularities on one or both surfaces.

In addition, it is preferable that the thickness of the electrolytic electrode base material 10 is 300 micrometers or less as mentioned above, It is more preferable that it is 205 micrometers or less, It is more preferable that it is 155 micrometers or less, It is further more preferable that it is 135 micrometers or less, 125 It is still more preferable that it is micrometer or less, It is still more preferable that it is 120 micrometers or less, It is still more preferable that it is 100 micrometers or less, It is further more preferable that it is 50 micrometers or less from a viewpoint of handling property and economy. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In the electrode base for electrolysis, it is preferable to relieve the residual stress at the time of processing by annealing the electrode base for electrolysis in an oxidizing atmosphere. Moreover, in order to improve the adhesiveness with the catalyst layer coat | covered with the said surface, the surface of an electrolytic electrode base material uses unevenness | corrugation using a steel grid, alumina powder, etc., and it is preferable to increase a surface area by acid treatment after that. Do. Or it is preferable to plating by the same element as a base material, and to increase a surface area.

In order to make the surface of the 1st layer 20 and the electrode base material 10 for electrolysis adhere to the electrode base material 10 for electrolysis, it is preferable to perform the process which increases a surface area. Examples of the treatment for increasing the surface area include a blast treatment using a cut wire, a steel grid, an alumina grid, and the like, an acid treatment using sulfuric acid or hydrochloric acid, a plating treatment using the same element as the substrate, and the like. Although arithmetic mean surface roughness Ra of the surface of a base material is not specifically limited, 0.05 micrometer-50 micrometers are preferable, 0.1-10 micrometers is more preferable, 0.1-8 micrometers is still more preferable.

Next, the case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

In FIG. 108, the 1st layer 20 which is a catalyst layer contains at least 1 sort (s) of oxide of ruthenium oxide, iridium oxide, and titanium oxide. Of ruthenium oxide RuO _2, etc., it may be mentioned. IrO ₂ etc. are mentioned as an iridium oxide. Examples of titanium oxides include TiO ₂ . The first layer 20 preferably contains two kinds of oxides of ruthenium oxide and titanium oxide, or three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide. Thereby, the 1st layer 20 becomes a more stable layer, and also adhesiveness with the 2nd layer 30 improves more.

In the case where the first layer 20 includes two kinds of oxides of ruthenium oxide and titanium oxide, titanium contained in the first layer 20 with respect to one mole of ruthenium oxide included in the first layer 20. It is preferable that it is 1-9 mol, and, as for an oxide, it is more preferable that it is 1-4 mol. By setting the composition ratio of the two kinds of oxides in this range, the electrolytic electrode 100 exhibits excellent durability.

When the first layer 20 includes three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide, the first layer 20 is included in the first layer 20 with respect to one mole of ruthenium oxide contained in the first layer 20. It is preferable that it is 0.2-3 mol, and, as for the iridium oxide used, it is more preferable that it is 0.3-2.5 mol. Moreover, it is preferable that it is 0.3-8 mol, and, as for 1 mol of titanium oxide contained in the 1st layer 20 with respect to 1 mol of ruthenium oxide contained in the 1st layer 20, it is more preferable. By making the composition ratio of three types of oxides into this range, the electrode 100 for electrolysis shows the outstanding durability.

When the 1st layer 20 contains at least 2 types of oxide chosen from a ruthenium oxide, an iridium oxide, and a titanium oxide, it is preferable that these oxides form a solid solution. By forming the oxide solid solution, the electrolytic electrode 100 exhibits excellent durability.

In addition to the above composition, as long as it contains at least one oxide of ruthenium oxide, iridium oxide and titanium oxide, those having various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like, referred to as DSA (registered trademark), may be used as the first layer 20.

The first layer 20 does not need to be a single layer, but may include a plurality of layers. For example, the first layer 20 may include a layer containing three kinds of oxides and a layer containing two kinds of oxides. 0.05-10 micrometers is preferable and, as for the thickness of the 1st layer 20, 0.1-8 micrometers is more preferable.

(2nd floor)

It is preferable that the 2nd layer 30 contains ruthenium and titanium. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

It is preferable that the 2nd layer 30 contains palladium oxide, the solid solution of palladium oxide, and platinum, or the alloy of palladium and platinum. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

The longer the longer the thickness of the second layer 30 can maintain the electrolytic performance, the thickness of the second layer 30 is preferably 0.05 to 3 m.

Next, the case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

As a component of the first layer 20 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal include at least one kind, the alloy containing the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide and the platinum group metal is platinum, palladium, rhodium, It is preferable to contain at least 1 type of platinum group metal among ruthenium and iridium.

As a platinum group metal, it is preferable to contain platinum.

It is preferable that a platinum group metal oxide contains ruthenium oxide.

It is preferable that a platinum group metal hydroxide contains a ruthenium hydroxide.

As a platinum group metal alloy, it is preferable to include the alloy of platinum, nickel, iron, and cobalt.

Moreover, it is preferable to contain the oxide or hydroxide of a lanthanoid element as a 2nd component as needed. As a result, the electrolytic electrode 100 exhibits excellent durability.

The oxide or hydroxide of the lanthanoid-based element preferably contains at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium.

Moreover, it is preferable to contain the oxide or hydroxide of a transition metal as a 3rd component as needed.

By adding the third component, the electrolytic electrode 100 exhibits more excellent durability and can reduce the electrolytic voltage.

Examples of preferred combinations include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + platinum + palladium Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium + Sulfur, Ruthenium + Lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + samarium + cobalt, ruthenium + samarium + gallium, ruthenium + samarium + gallium, ruthenium + Samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + Nickel + palladium, bag Gold + nickel + ruthenium, an alloy of platinum and nickel, an alloy of platinum and cobalt, an alloy of platinum and iron, and the like.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal are not included, the main component of the catalyst is preferably nickel element.

It is preferable to contain at least 1 sort (s) among nickel metal, oxide, and hydroxide.

You may add a transition metal as a 2nd component. As a 2nd component to add, it is preferable to contain at least 1 type of element among titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon.

As a preferable combination, nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, etc. are mentioned.

If necessary, an intermediate layer can be formed between the first layer 20 and the electrolytic electrode substrate 10. By providing the intermediate layer, the durability of the electrolytic electrode 100 can be improved.

As an intermediate | middle layer, what has affinity for both the 1st layer 20 and the electrode base material 10 for electrolysis is preferable. As the intermediate layer, nickel oxide, platinum group metal, platinum group metal oxide, and platinum group metal hydroxide are preferable. As an intermediate | middle layer, it can form by apply | coating and baking the solution containing the component which forms an intermediate | middle layer, and can also form a surface oxide layer by heat-processing a base material at 300-600 degreeC in air atmosphere. In addition, it can form by a well-known method, such as a thermal spraying method and an ion plating method.

(2nd floor)

As the components of the first layer 30 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included. Examples of preferred combinations of the elements included in the second layer include combinations exemplified in the first layer. The combination of a 1st layer and a 2nd layer may be a combination with the same composition, and a composition ratio differs, and the combination of a different composition may be sufficient as it.

As thickness of a catalyst layer, the sum total of the formed catalyst layer and the intermediate | middle layer has preferable 0.01 micrometer-20 micrometers. If it is 0.01 micrometer or more, it can fully function as a catalyst. If it is 20 micrometers or less, a strong catalyst layer can be formed with little fall-out from a base material. 0.05 micrometers-15 micrometers are more preferable. More preferably, they are 0.1 micrometer-10 micrometers. More preferably, they are 0.2 micrometer-8 micrometers.

As thickness of an electrode, ie, the thickness of the sum total of an electrolytic electrode base material and a catalyst layer, 315 micrometers or less are preferable, 220 micrometers or less are more preferable, 170 micrometers or less are more preferable from a viewpoint of handling property of an electrode, 150 The thickness is even more preferable, 145 µm or less is particularly preferable, 140 µm or less is still more preferable, 138 µm or less is even more preferable, and 135 µm or less is even more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, it is preferable that it is 130 micrometers or less from a viewpoint similar to the above, More preferably, it is less than 130 micrometers, More preferably, it is 115 micrometers or less, More preferably, it is 65 micrometers or less. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, the thickness of an electrode can be calculated | required by measuring with a dejimatic thickness gauge (Mitsutoyo Corporation, minimum display 0.001 mm). The thickness of the electrode base material for electrodes is measured similarly to electrode thickness. The catalyst layer thickness can be obtained by subtracting the thickness of the electrode base material for electrolysis from the electrode thickness.

In the present embodiment, from the viewpoint of securing sufficient electrolytic performance, the electrode for electrolysis is Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y , Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd It is preferred to include at least one catalyst component selected from the group consisting of Pm, Sm, Eu, Gd, Tb and Dy.

In the present embodiment, the electrode for electrolysis can obtain better handling property as long as it is an electrode having a large elastic deformation region, and has better adhesion force such as a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, a catalyst-free feeder, and the like. From the viewpoint of having a thickness, the thickness of the electrode for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, still more preferably 170 µm or less, even more preferably 150 µm or less, and particularly 145 µm or less. Preferably, 140 micrometers or less are further more preferable, 138 micrometers or less are further more preferable, 135 micrometers or less are further more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, from a viewpoint similar to the above, 130 micrometers or less are preferable, less than 130 micrometers are more preferable, 115 micrometers or less are more preferable, and 65 micrometers or less are still more preferable. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, in this embodiment, a "elastic deformation area | region is wide" means that it is difficult to produce the curvature resulting from winding after winding an electrode for electrolysis to make a winding body, and canceling a wound state. In addition, the thickness of an electrode for electrolysis means the thickness which combined the electrode base material for electrolysis and a catalyst layer, when including the catalyst layer mentioned later.

(Method for producing electrode for electrolysis)

Next, one Embodiment of the manufacturing method of the electrolytic electrode 100 is described in detail.

In the present embodiment, the first layer 20, preferably the second layer (on the electrode base material for electrolysis) is performed by a method such as baking (pyrolysis) of the coating film in an oxygen atmosphere or ion plating, plating, thermal spraying or the like. By forming 30), the electrode 100 for electrolysis can be manufactured. In this manufacturing method of the present embodiment, high productivity of the electrode 100 for electrolysis can be realized. Specifically, a catalyst layer is formed on the electrode base material for electrolysis by a coating step of applying a coating liquid containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing pyrolysis. Pyrolysis means here that the metal salt used as a precursor is heated and decomposed | disassembled into a metal or metal oxide and gaseous substance. Although decomposition products differ depending on the metal species used, the kind of salt, and the atmosphere in which pyrolysis is performed, most metals tend to form oxides in an oxidizing atmosphere. In the industrial production process of electrodes, pyrolysis is usually carried out in air, and in most cases metal oxides or metal hydroxides are formed.

(Formation of the first layer of the anode)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved at least 1 sort (s) of metal salt of ruthenium, iridium, and titanium to an electrolytic electrode base material, and thermally decomposes (baking) in presence of oxygen. The content of ruthenium, iridium and titanium in the first coating liquid is approximately the same as that of the first layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of the second layer)

The 2nd layer 30 is formed as needed, for example, apply | coating the solution containing a palladium compound and a platinum compound, or the solution (2nd coating liquid) containing a ruthenium compound and a titanium compound on the 1st layer 20 After that, it is obtained by pyrolysis in the presence of oxygen.

(Formation of First Layer of Cathode by Pyrolysis)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved the metal salt of various combinations to the electrode base material for electrolysis, and thermally decomposing (baking) in presence of oxygen. The content rate of the metal in a 1st coating liquid is substantially the same as the 1st layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of intermediate layer)

An intermediate | middle layer is formed as needed, for example, is obtained by apply | coating the solution (2nd coating liquid) containing a palladium compound or a platinum compound on a base material, and then thermally decomposing in presence of oxygen. Alternatively, the nickel oxide intermediate layer may be formed on the surface of the substrate only by heating the substrate without applying the solution.

(Formation of First Layer of Cathode by Ion Plating)

The first layer 20 may be formed by ion plating.

As an example, the method of fixing a base material in a chamber, and irradiating an electron beam to a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and ruthenium is deposited on the substrate as ruthenium oxide.

(Formation of First Layer of Cathode by Plating)

The first layer 20 can also be formed by a plating method.

As an example, when a base material is used as a cathode and electrolytic plating is performed in the electrolyte solution containing nickel and tin, alloy plating of nickel and tin can be formed.

(Formation of First Layer of Cathode by Thermal Spray)

The first layer 20 can also be formed by thermal spraying.

As an example, by spraying nickel oxide particles on a substrate, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed.

Hereinafter, the ion exchange membrane which concerns on one aspect of a diaphragm is explained in full detail.

[Ion exchange membrane]

The ion exchange membrane is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various ion exchange membranes can be applied. In this embodiment, it is preferable to use the membrane main body containing the hydrocarbon type polymer or fluorine-containing polymer which has an ion exchange group, and the ion exchange membrane which has a coating layer formed on at least one surface of this membrane main body. In addition, it is preferable that the coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is 0.1-10 m 2 / g. The ion-exchange membrane of such a structure has little influence on the electrolytic performance by the gas which generate | occur | produces during electrolysis, and it tends to exhibit stable electrolytic performance.

The membrane of the perfluorocarbon polymer into which the ion exchange group is introduced is a sulfonic acid layer having an ion exchange group derived from a sulfo group (group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and an ion exchange group derived from a carboxyl group. It is provided with either a carboxylic sancheung having a - (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). In view of strength and dimensional stability, it is preferable to further have a reinforcing core material.

The inorganic particles and the binder will be described in detail in the description section of the coating layer below.

109 is a schematic sectional view showing an embodiment of the ion exchange membrane. The ion exchange membrane 1 has a membrane main body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group, and coating layers 11a and 11b formed on both surfaces of the membrane main body 10.

In the ion exchange membrane 1, the membrane main body 10 is a sulfonic acid layer 3 having an ion exchange group derived from a sulfo group (a group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and ions derived from a carboxyl group. exchanger has a strength and dimensional stability are enhanced by the carboxylic sancheung 2 provided, and the reinforcement core (4) having a (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). Since the ion exchange membrane 1 is provided with the sulfonic acid layer 3 and the carboxylic acid layer 2, it is suitably used as a cation exchange membrane.

In addition, the ion exchange membrane may have only one of a sulfonic acid layer and a carboxylic acid layer. In addition, the ion exchange membrane does not necessarily need to be reinforced by the reinforcing core, and the arrangement state of the reinforcing core is not limited to the example of FIG. 109.

(The membrane body)

First, the membrane main body 10 constituting the ion exchange membrane 1 will be described.

The membrane main body 10 may have a function of selectively permeating cations, and may include a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group. The structure and the material thereof are not particularly limited, and a suitable one can be appropriately selected. have.

The hydrocarbon-based polymer or fluorine-containing polymer having an ion exchange group in the membrane main body 10 can be obtained from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange precursor which can be an ion-exchange group, for example, by hydrolysis or the like. Specifically, for example, the main chain is made of a fluorinated hydrocarbon, and has a group (ion exchanger precursor) which can be converted into an ion exchanger by hydrolysis or the like as a pendant side chain, and also a polymer which can be melt processed (hereinafter referred to as "fluorine-containing polymer). (a) ") to produce the precursor of the membrane main body 10, and then convert the ion exchanger precursor into the ion exchanger to obtain the membrane main body 10.

The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the third group below. have. Moreover, it can also manufacture by the homopolymerization of 1 type of monomers chosen from any of the following 1st group, the following 2nd group, and the following 3rd group.

As a monomer of a 1st group, a vinyl fluoride compound is mentioned, for example. Examples of the vinyl fluoride compound include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and the like. In particular, when the ion exchange membrane is used as the alkali electrolytic membrane, the vinyl fluoride compound is preferably a perfluoro monomer, and is perfluoro selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Monomer is preferred.

As a monomer of a 2nd group, the vinyl compound which has a functional group which can be converted into a carboxylic acid type ion exchange group (carboxylic acid group) is mentioned, for example. Of a vinyl compound having a functional group that can be converted to a carboxylic acid group, for example, and the like can be _{CF 2 = CF (OCF 2 CYF} ) s -O (CZF) t monomers represented by -COOR (wherein, s is 0 An integer of -2, t represents an integer of 1 to 12, Y and Z each independently represents F or CF ₃ , and R represents a lower alkyl group, for example, a lower alkyl group is an alkyl group having 1 to 3 carbon atoms. .).

Among these, CF is _{2 = CF (OCF 2 CYF)} n -O (CF 2) _m -COOR compound represented by are preferred. Here n represents an integer of 0 to 2, m represents an integer of 1 to 4, Y represents F or CF ₃ , and R represents CH ₃ , C ₂ H ₅ or C ₃ H ₇ .

When the ion exchange membrane is used as a cation exchange membrane for alkali electrolysis, it is preferable to use at least a perfluoro compound as the monomer. However, since the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis, the alkyl group ( R) may not be a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

As a monomer of a 2nd group, the monomer shown below is more preferable among the above.

CF ₂ = CFOCF ₂ -CF (CF ₃ ) OCF ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CF [OCF ₂ -CF (CF ₃ )] ₂ O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₃ COOCH ₃ .

As a monomer of a 3rd group, the vinyl compound which has a functional group which can be converted into a sulfone type ion exchange group (sulfonic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted into a sulfonic acid is, for example, CF ₂ = a monomer represented by the _{CFO-X-CF 2 -SO 2} F are preferred (wherein, X represents an alkylene group of a perfluoroalkyl.). As these specific examples, the monomer etc. which are shown below are mentioned.

CF ₂ = CFOCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CF (CF ₂ ) ₂ SO ₂ F,

CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₂ OCF ₃ ) OCF ₂ CF ₂ SO ₂ F.

Among these, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F are more preferable.

The copolymer obtained from these monomers can be manufactured by the polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, especially the general polymerization method used with respect to tetrafluoroethylene. For example, in the non-aqueous method, inert solvents such as perfluorohydrocarbon and chlorofluorocarbon are used, and in the presence of radical polymerization initiators such as perfluorocarbon peroxide and azo compound, the temperature is 0 to 200 캜 and the pressure is 0.1 to 0.1. The polymerization reaction can be carried out under the condition of 20 MPa.

In the said copolymerization, the kind and ratio of the combination of the said monomers are not specifically limited, It selects according to the kind and quantity of the functional group to provide to the fluorine-containing polymer obtained. For example, in the case of using a fluorine-containing polymer containing only a carboxylic acid group, at least one monomer may be selected and copolymerized from the first group and the second group, respectively. In the case of using a fluorine-containing polymer containing only a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group and the third group, respectively. In the case of using a fluorine-containing polymer having a carboxylic acid group and a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group, the second group, and the third group, respectively. In this case, the target fluorine-containing polymer can also be obtained by separately polymerizing the copolymer composed of the first group and the second group and the copolymer composed of the first group and the third group, and then mixing the copolymer separately. . Moreover, although the mixing ratio of each monomer is not specifically limited, When increasing the quantity of functional groups per unit polymer, what is necessary is just to increase the ratio of the monomer chosen from the said 2nd group and the 3rd group.

Although the total ion exchange capacity of a fluorine-containing copolymer is not specifically limited, It is preferable that it is 0.5-2.0 mg equivalent / g, and it is more preferable that it is 0.6-1.5 mg equivalent / g. Here, total ion exchange capacity means the equivalent of the exchanger per unit weight of dry resin, and can be measured by neutralization titration etc.

In the membrane main body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorine-containing polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorine-containing polymer having a carboxylic acid group are laminated. . By using this layer structure as the membrane main body 10, the selective permeability of cations such as sodium ions can be further improved.

In the case where the ion exchange membrane 1 is disposed in the electrolytic cell, the sulfonic acid layer 3 is usually disposed on the anode side of the electrolytic cell and the carboxylic acid layer 2 on the cathode side of the electrolytic cell.

It is preferable that the sulfonic acid layer 3 is comprised from the material with low electrical resistance, and it is preferable that a film thickness is thicker than the carboxylic acid layer 2 from a viewpoint of film strength. The film thickness of the sulfonic acid layer 3 becomes like this. Preferably it is 2-25 times of the carboxylic acid layer 2, More preferably, it is 3-15 times.

It is preferable that the carboxylic acid layer 2 has high anion exclusion property even if it is thin. Anion-exclusion here means the property which wants to interrupt the invasion and permeation | transmission of anion to the ion exchange membrane 1. In order to improve anion exclusion, disposing a carboxylic acid layer having a small ion exchange capacity with respect to the sulfonic acid layer is effective.

As the fluorine-containing polymer used for the sulfonic acid layer 3, for example, a polymer obtained by using CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F as the third group of monomers is suitable.

Carboxylic acids referred to as the fluorine-based polymer for use in sancheung (2) is, for example, as monomers of group 2 _{CF 2 = CFOCF 2 CF (CF} 2) O (CF 2) a polymer obtained by using ₂ COOCH ₃ are suitable.

(Coating layer)

It is preferable that an ion exchange membrane has a coating layer on at least one surface of a membrane main body. 109, in the ion exchange membrane 1, the coating layers 11a and 11b are formed on both surfaces of the membrane main body 10, respectively.

The coating layer includes inorganic particles and a binder.

As for the average particle diameter of an inorganic particle, it is more preferable that it is 0.90 micrometer or more. If the average particle diameter of the inorganic particles is 0.90 µm or more, the durability against impurities as well as gas adhesion is greatly improved. In other words, a particularly significant effect is obtained by increasing the average particle diameter of the inorganic particles and by satisfying the above-described specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by crushing gemstones can be used. Preferably, the inorganic particles obtained by gemstone grinding can be suitably used.

In addition, the average particle diameter of an inorganic particle can be 2 micrometers or less. If the average particle diameter of an inorganic particle is 2 micrometers or less, it can prevent that a film | membrane is damaged by an inorganic particle. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 µm.

Here, an average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation).

It is preferable that the shape of an inorganic particle is an irregular shape. Resistance to impurities is further improved. In addition, the particle size distribution of the inorganic particles is preferably wide.

It is preferable that an inorganic particle contains at least 1 sort (s) of inorganic substance chosen from the group which consists of an oxide of a group IV element of a periodic table, a nitride of a group IV element of a periodic table, and a carbide of a group IV element of a periodic table. More preferably, they are particles of zirconium oxide from the viewpoint of durability.

It is preferable that this inorganic particle is an inorganic particle manufactured by crushing the gemstone of an inorganic particle, or it is preferable to make spherical particle | grains of the uniform diameter of particle | grains into an inorganic particle by melting and refine | purifying the gemstone of an inorganic particle.

Examples of the raw material grinding method include, but are not particularly limited to, ball mills, bead mills, colloid mills, conical mills, disc mills, edge mills, milling mills, hammer mills, pellet mills, VSI mills, willy mills, roller mills, and jet mills. Etc. can be mentioned. Moreover, it is preferable to wash | clean after grinding | pulverization, and it is preferable to be acid-processed at that time. As a result, impurities such as iron adhering to the surface of the inorganic particles can be reduced.

The coating layer preferably comprises a binder. A binder is a component which keeps inorganic particle on the surface of an ion exchange membrane, and comprises a coating layer. It is preferable that a binder contains a fluorine-containing polymer from a viewpoint of resistance to electrolyte solution or the product by electrolysis.

As a binder, it is more preferable that it is a fluorine-containing polymer which has a carboxylic acid group or a sulfonic acid group from a tolerance with respect to the electrolyte solution and the product by electrolysis, and adhesiveness to the surface of an ion exchange membrane. When forming a coating layer on the layer (sulfonic acid layer) containing a fluorine-containing polymer which has a sulfonic acid group, it is more preferable to use the fluorine-containing polymer which has a sulfonic acid group as a binder of this coating layer. Moreover, when forming a coating layer on the layer (carboxylic acid layer) containing the fluorine-containing polymer which has a carboxylic acid group, it is more preferable to use the fluorine-containing polymer which has a carboxylic acid group as a binder of this coating layer.

It is preferable that it is 40-90 mass%, and, as for content of an inorganic particle in a coating layer, it is more preferable that it is 50-90 mass%. Moreover, it is preferable that it is 10-60 mass%, and, as for content of a binder, it is more preferable that it is 10-50 mass%.

The distribution density of the coating layer in the ion exchange membrane is preferably 0.05 to 2 mg per cm 2. In addition, when an ion exchange membrane has a concave-convex shape on the surface, it is preferable that the distribution density of a coating layer is 0.5-2 mg per cm <2>.

It does not specifically limit as a method of forming a coating layer, A well-known method can be used. For example, the method of apply | coating the coating liquid which disperse | distributed inorganic particle to the solution containing a binder by spray etc. is mentioned.

(Reinforced heartwood)

It is preferable that the ion exchange membrane has a reinforcing core material disposed inside the membrane body.

The reinforcing core is a member for enhancing the strength and dimensional stability of the ion exchange membrane. By arrange | positioning a reinforcing core material inside a membrane main body, especially expansion and contraction of an ion exchange membrane can be controlled to a desired range. Such an ion exchange membrane can maintain excellent dimensional stability for a long time without being stretched more than necessary in electrolysis or the like.

The configuration of the reinforcing core is not particularly limited, and may be formed by spinning a yarn called reinforcing yarn, for example. The reinforcement yarn mentioned here is a member which constitutes a reinforcing core material, which can impart desired dimensional stability and mechanical strength to the ion exchange membrane, and refers to a yarn that can stably exist in the ion exchange membrane. By using the reinforcing core material which radiated such reinforcement yarn, further excellent dimensional stability and mechanical strength can be provided to the ion exchange membrane.

The material of the reinforcing core material and the reinforcing yarn used for this is not particularly limited, but it is preferable that the material is resistant to acids, alkalis, or the like. desirable.

Examples of the fluorine-containing polymer used in the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether polymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetra Fluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, vinylidene fluoride polymer (PVDF), and the like. Among these, it is preferable to use the fiber which consists of polytetrafluoroethylene from a heat resistant and chemical resistant viewpoint especially.

The diameter of the reinforcing sand used for the reinforcing core is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The weave density (number of insertion lines per unit length) is preferably 5 to 50 lines / inch. The form of the reinforcing core is not particularly limited, and for example, a woven fabric, a nonwoven fabric, a knitted fabric, or the like is used, but it is preferably a form of a woven fabric. In addition, the thickness of the woven fabric is preferably 30 to 250 m, more preferably 30 to 150 m.

As the woven fabric or knitted fabric, monofilament, multifilament or yarns, slit yarns, and the like thereof can be used, and the weaving method can use various weaving methods such as plain weave, leno weave, knitting, cord weave, and seerker.

The weaving method and arrangement of the reinforcing core material in the membrane main body are not particularly limited and can be appropriately arranged in consideration of the size and shape of the ion exchange membrane, the desired physical properties and the use environment for the ion exchange membrane, and the like.

For example, the reinforcing core may be disposed along a predetermined direction of the membrane body, but from the viewpoint of dimensional stability, the reinforcing core is disposed along the predetermined first direction, and a second direction substantially perpendicular to the first direction is provided. Therefore, it is preferable to arrange a separate reinforcing core material. By arranging the plurality of reinforcing cores so as to run substantially straight inside the longitudinal membrane body of the membrane body, further superior dimensional stability and mechanical strength can be imparted in multiple directions. For example, an arrangement for weaving the reinforcing core material (warp) disposed along the longitudinal direction and the reinforcing core material (weft) arranged along the transverse direction on the surface of the membrane body is preferable. Lion weaved by inserting the same number of wefts into the weaving plain weave by twisting and inserting warp and weft alternately, or by weaving two warp and leno weaving by twisting two warp and two or several lines. It is more preferable to use a woven fabric (a loom) from the viewpoint of dimensional stability, mechanical strength, and ease of manufacture.

In particular, it is preferable that the reinforcing core is disposed along both directions of the MD direction (Machine Direction direction) and the TD direction (Transverse Direction direction) of the ion exchange membrane. That is, it is preferable to be woven in the MD direction and the TD direction. Here, MD direction means the direction (flow direction) in which a membrane main body and various core materials (for example, a reinforced core material, a reinforcement yarn, a sacrificial yarn etc. mentioned later) are conveyed in the manufacturing process of the ion exchange membrane mentioned later, and a TD direction is It refers to a direction approximately perpendicular to the MD direction. The yarn woven along the MD direction is called MD yarn, and the yarn woven along the TD direction is called TD yarn. Usually, the ion exchange membrane used for electrolysis is rectangular, and a longitudinal direction becomes MD direction, and the width direction becomes a TD direction in many cases. By weaving the reinforced MD core material and the reinforced TD core material, it is possible to give even more excellent dimensional stability and mechanical strength in multiple directions.

The spacing of the reinforcing cores is not particularly limited and can be appropriately arranged in consideration of desired physical properties, use environment, and the like for the ion exchange membrane.

The opening ratio of the reinforcing core material is not particularly limited, and is preferably 30% or more, more preferably 50% or more and 90% or less. The opening ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane.

The opening ratio of the reinforcing core is the total area (B) of the surface through which substances such as ions (electrolyte and cation (for example, sodium ions) contained) in the area (A) of either surface of the membrane body can pass. The ratio of (B / A). The total area (B) of the surface through which substances such as ions can pass can be referred to as the total area of the region where cations, electrolytes, and the like are not blocked by the reinforcing core included in the ion exchange membrane.

110 is a schematic view for explaining the aperture ratio of the reinforcing core material constituting the ion exchange membrane. 110 enlarges a part of the ion exchange membrane and shows only the arrangement of the reinforcing core materials 21 and 22 in the region, and the illustration of the other members is omitted.

The total area C of the reinforcement core from the area A of the region including the area of the reinforcement core, which is also surrounded by the reinforcement core 21 arranged in the longitudinal direction and the reinforcement core 22 arranged in the horizontal direction. By subtracting, the total area B of the area through which substances such as ions in the area A of the area can pass can be obtained. That is, an opening ratio can be calculated | required by following formula (I).

Aperture ratio = (B) / (A) = ((A)-(C)) / (A). (I)

Among the reinforcing cores, a particularly preferable form is a tape yarn or a highly oriented monofilament containing PTFE in view of chemical resistance and heat resistance. Specifically, a high-strength porous sheet made of PTFE is a tape yarn slitted in tape form, or a 50 to 300 denier of a highly oriented monofilament made of PTFE, and a woven density of 10 to 50 lines / inch. It is more preferable that it is a reinforcement core material whose thickness is the range of 50-100 micrometers. It is more preferable that the opening ratio of the ion exchange membrane including such a reinforcing core material is 60% or more.

Examples of the shape of the reinforcing yarn include round yarns and tape-like yarns.

(Communication hole)

It is preferable that the ion exchange membrane has a communication hole inside the membrane main body.

The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, a communication hole is a tubular hole formed in the inside of a membrane main body, and is formed by eluting the sacrificial core material (or sacrificial thread) mentioned later. The shape and diameter of the communication hole can be controlled by selecting the shape and diameter of the sacrificial core material (sacrificial yarn).

By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured at the time of electrolysis. Although the shape of a communication hole is not specifically limited, According to the manufacturing method mentioned later, it can be set as the shape of the sacrificial core material used for formation of a communication hole.

The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With such a structure, in the part where the communication hole is formed in the cathode side of the reinforcing core material, ions (for example, sodium ions) transported through the electrolyte solution filled in the communication hole can also flow to the cathode side of the reinforcing core material. As a result, since the flow of cation is not blocked, the electrical resistance of the ion exchange membrane can be made lower.

The communication hole may be formed along only one predetermined direction of the membrane main body constituting the ion exchange membrane, but is formed in both the longitudinal direction and the transverse direction of the membrane main body in view of exhibiting more stable electrolytic performance. desirable.

[Production method]

As a suitable manufacturing method of an ion exchange membrane, the method of having the following (1) process-(6) process is mentioned.

(1) Process: The process of manufacturing the fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(2) Process: If necessary, a sacrificial yarn is disposed between adjacent reinforcing cores by at least weaving a plurality of reinforcing cores and a property of dissolving in an acid or alkali and forming at least a communication hole. To obtain the finished reinforcement.

(3) Process: The process of film-forming the said fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(4) Step: The step of embedding the reinforcing material in the film as necessary to obtain a membrane body having the reinforcing material disposed therein.

(5) Process: The process (hydrolysis process) of hydrolyzing the membrane main body obtained at process (4).

(6) Process: The process (coating process) of forming a coating layer in the film main body obtained at the process (5).

Hereinafter, each process is explained in full detail.

(1) Process: process for producing fluorine-containing polymer

In the step (1), the fluorine-containing polymer is produced by using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of a fluorine-containing polymer, in the manufacture of the fluorine-containing polymer which forms each layer, the mixing ratio of the monomer of a raw material may be adjusted.

(2) Process: manufacturing process of reinforcement

A reinforcing material is a woven fabric etc. which woven the reinforcement yarn. The reinforcing material is embedded in the film to form the reinforcing core material. When using an ion exchange membrane having communication holes, the sacrificial yarn is also woven into the reinforcing material. In this case, the blending amount of the sacrificial material is preferably 10 to 80 mass%, more preferably 30 to 70 mass% of the entire reinforcing material. By weaving a sacrificial thread, the mesh shift | offset of a reinforcement core material can also be prevented.

The sacrificial material has solubility in a film production process or an electrolytic environment, and rayon, polyethylene terephthalate (PET), cellulose, polyamide, and the like are used. Moreover, polyvinyl alcohol etc. which have a thickness of 20-50 denier and consist of monofilament or multifilament are also preferable.

In the step (2), by adjusting the arrangement of the reinforcing core material or the sacrificial material, the opening ratio, the arrangement of the communication holes, and the like can be controlled.

(3) process: filming process

In the step (3), the fluorine-containing polymer obtained in the step (1) is filmed using an extruder. A single layer structure may be sufficient as a film, and as above-mentioned, the two-layered structure of a sulfonic acid layer and a carboxylic acid layer may be sufficient, and the multilayered structure of three or more layers may be sufficient as it.

As a method of film-forming, the following are mentioned, for example.

A method of filming each of the fluorine-containing polymer having a carboxylic acid group and the fluorine-containing polymer having a sulfonic acid group separately.

A method in which a fluorine-containing polymer having a carboxylic acid group and a fluorine-containing polymer having a sulfonic acid group are co-extruded into a composite film.

In addition, a plurality of films may be sufficient respectively. Moreover, coextrusion of different kinds of films is preferable because it contributes to raising the adhesive strength of an interface.

(4) step: the step of obtaining the membrane body

In the step (4), the film body in which the reinforcing material is embedded is obtained by embedding the reinforcing material obtained in the step (2) inside the film obtained in the step (3).

As a preferable formation method of a film main body, (i) the fluorine-containing polymer which has a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) located in the cathode side (henceforth, the layer which consists of this is called a 1st layer), And forming a fluorine-containing polymer having a sulfonic acid group precursor (e.g., a sulfonylfluoride functional group) (hereinafter, referred to as a second layer) by a coextrusion method, and heating and vacuum source as necessary. Is laminated on a flat plate or drum having a large number of pores on the surface of the reinforcing material and the second layer / first layer composite film in the order of a reinforcing material and a heat-resistant release paper having air permeability. Integrating while removing air between each layer by decompression under temperature; (ii) Apart from the second layer / first layer composite film, the fluorine-containing polymer (third layer) having a sulfonic acid group precursor is previously filmed alone, and the surface is heated and heated using a vacuum source if necessary. The laminated film was laminated in the order of a composite film consisting of a third layer film, a reinforcing core material, and a second layer / first layer via a heat-resistant release paper having air permeability on a flat plate or a drum having a large number of pores thereon. The method of integrating, removing the air between each layer by pressure reduction under the temperature which melt | dissolves is mentioned.

Here, coextrusion of a 1st layer and a 2nd layer contributes to raising the adhesive strength of an interface.

Moreover, the method of integrating under reduced pressure has the feature that the thickness of the 3rd layer on a reinforcement material becomes large compared with the pressure press method. In addition, since the reinforcing material is fixed to the inner surface of the membrane main body, it has the performance of sufficiently maintaining the mechanical strength of the ion exchange membrane.

In addition, the variation of lamination described here is an example, and considering the desired layer structure, physical properties, etc. of a film body, a suitable lamination pattern (for example, the combination of each layer, etc.) can be selected, and then co-extruded.

Further, in order to further improve the electrical performance of the ion exchange membrane, a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is further interposed between the first layer and the second layer. It is also possible to use a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor instead of the layer.

The method for forming the fourth layer may be a method of separately preparing a fluorine-containing polymer having a carboxylic acid group precursor and a fluorine-containing polymer having a sulfonic acid group precursor, and then mixing the monomers with the carboxylic acid group precursor and the sulfonic acid group precursor. The method of copolymerizing the monomer which has the thing may be used.

In the case where the fourth layer is configured as an ion exchange membrane, the coextruded film of the first layer and the fourth layer is molded, and the third layer and the second layer are filmed independently of this, by the method described above. You may laminate | stack and three layers of a 1st layer / 4th layer / 2nd layer may be film-formed by coextrusion at once.

In this case, the direction in which the extruded film flows is the MD direction. In this way, a membrane body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material.

In addition, the ion exchange membrane preferably has a protruding portion, that is, a convex portion, made of a fluorine-containing polymer having a sulfonic acid group, on the surface side of the sulfonic acid layer. It does not specifically limit as a method of forming such a convex part, The well-known method of forming a convex part in the resin surface can be employ | adopted. Specifically, the method of embossing on the surface of a film main body is mentioned, for example. For example, when the said composite film, reinforcing material, etc. are integrated, the said convex part can be formed by using the release paper previously embossed. When forming a convex part by embossing, control of the height and placement density of a convex part can be performed by controlling the emboss shape (shape of a release paper) to be transferred.

(5) hydrolysis process

In the step (5), the membrane body obtained in the step (4) is hydrolyzed to convert the ion exchanger precursor into the ion exchanger (hydrolysis step).

In the step (5), the elution hole can be formed in the membrane main body by dissolving and removing the sacrificial yarn contained in the membrane main body with an acid or an alkali. In addition, the sacrificial yarn may remain in the communication hole without being completely dissolved and removed. In addition, the sacrificial yarn remaining in the communication hole may be dissolved and removed by the electrolytic solution when the ion exchange membrane is provided for electrolysis.

The sacrificial yarn is soluble in acid or alkali in the ion exchange membrane production process or in an electrolytic environment, and communication holes are formed in the site by dissolving the sacrificial material.

The step (5) can be performed by immersing the membrane body obtained in the step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (dimethyl sulfoxide) can be used.

It is preferable that the said mixed solution contains 2.5-4.0 N of KOH, and contains 25-35 mass% of DMSO.

As temperature of hydrolysis, it is preferable that it is 70-100 degreeC. The higher the temperature, the thicker the apparent thickness. More preferably, it is 75-100 degreeC.

It is preferable that it is 10 to 120 minutes as time of hydrolysis. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes.

Here, the process of forming a communication hole by eluting a sacrificial yarn is demonstrated in detail. 111 (a) and 111 (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane.

In FIGS. 111A and 111B, only the communication holes 504 formed by the reinforcement yarn 52, the sacrificial yarn 504a, and the sacrificial yarn 504a are shown. The illustration is omitted.

First, the reinforcement yarn 52 which comprises a reinforcing core material in an ion exchange membrane, and the sacrificial yarn 504a for forming the communication hole 504 in an ion exchange membrane are used as a knitted reinforcement material. And the communication hole 504 is formed by eluting the sacrificial yarn 504a in the process (5).

According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a may be adjusted in accordance with the arrangement of the reinforcing core and the communication hole in the membrane main body of the ion exchange membrane.

In (a) of FIG. 111, although the reinforcement of the plain weave which woven the reinforcement yarn 52 and the sacrificial yarn 504a in both the longitudinal direction and the horizontal direction in the ground is illustrated, the reinforcement yarn in a reinforcement material as needed. The arrangement of the 52 and the victim 504a can be changed.

(6) coating process

In the step (6), the coating layer can be formed by preparing a coating liquid containing the inorganic particles obtained by gemstone grinding or melting of the gemstone and a binder, and applying and drying the coating liquid on the surface of the ion exchange membrane obtained in the step (5). .

As a binder, after hydrolyzing the fluorine-containing polymer having an ion exchange group precursor with an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH), it is immersed in hydrochloric acid to replace the counter ion of the ion exchange group with H ⁺ . One binder (eg, a fluorine-containing polymer having a carboxyl or sulfo group) is preferred. Since it becomes easy to melt | dissolve in water and ethanol mentioned later by this, it is preferable.

This binder is dissolved in a solution in which water and ethanol are mixed. Moreover, the preferable volume ratio of water and ethanol is 10: 1-1:10, More preferably, it is 5: 1-1: 5, More preferably, it is 2: 1-1: 2. In the solution thus obtained, the inorganic particles are dispersed by a ball mill to obtain a coating solution. At this time, the average particle diameter of a particle | grains, etc. can also be adjusted by adjusting the time and the rotation speed at the time of dispersion. In addition, the preferable compounding quantity of an inorganic particle and a binder is as above-mentioned.

The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, but is preferably a light coating liquid. Thereby, it becomes possible to apply | coat uniformly to the surface of an ion exchange membrane.

In addition, when dispersing the inorganic particles, a surfactant may be added to the dispersion. As surfactant, a nonionic surfactant is preferable, For example, HS-210, NS-210, P-210, E-212 by Nichi-yu Corporation, etc. are mentioned.

An ion exchange membrane is obtained by apply | coating the obtained coating liquid to the surface of an ion exchange membrane by spray coating or roll coating.

[Microporous membrane]

As described above, the microporous membrane of the present embodiment is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various microporous membranes can be applied.

Although the porosity of the microporous membrane of this embodiment is not specifically limited, For example, it can be 20-90, Preferably it is 30-85. The porosity can be calculated by the following formula, for example.

Porosity = (1- (Dry Film Weight in Dry State) / (Volume calculated from the thickness, width and length of the film and weight calculated from the density of the film material)) × 100

Although the average pore diameter of the microporous membrane of this embodiment is not specifically limited, For example, it can be 0.01 micrometer-10 micrometers, Preferably it is 0.05 micrometer-5 micrometers. The average pore diameter is, for example, the film is vertically cut in the thickness direction, and the cut surface is observed by FE-SEM. It can obtain | require by measuring and averaging about 100 points of the diameter of the hole observed.

Although the thickness of the microporous film of this embodiment is not specifically limited, For example, it can be 10 micrometers-1000 micrometers, Preferably it is 50 micrometers-600 micrometers. The said thickness can be measured using a micrometer (made by Mitsutoyo Corporation) etc., for example.

Specific examples of the microporous membranes described above include Agir's Zirfon Perl UTP 500 (also referred to as Zirfon membrane in this embodiment), International Publication No. 2013-183584, International Publication No. 2016-203701, etc. The things described are mentioned.

In this embodiment, it is preferable that a diaphragm contains the 1st ion exchange resin layer and the 2nd ion exchange resin layer which has EW (ion exchange equivalent) different from this 1st ion exchange resin layer. Moreover, it is preferable that a diaphragm contains the 1st ion exchange resin layer and the 2nd ion exchange resin layer which has a functional group different from this 1st ion exchange resin layer. An ion exchange equivalent can be adjusted with the functional group to introduce | transduce, and the functional group which can be introduce | transduced is as above-mentioned.

(Hydraulic)

As the electrolytic cell in this embodiment, the electrolytic cell in the case of performing electrolysis has a structure which changed the ion exchange membrane in the electrolytic cell in the case of performing the above-mentioned salt electrolysis to a microporous membrane. In addition, since the raw material to be supplied is water, it differs from the electrolytic cell in the case of performing the above-mentioned salt electrolysis. As for other configurations, the same configuration as the electrolytic cell in the case of performing salt electrolysis can also be adopted. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. However, in the case of hydrolysis, since oxygen gas is only generated in the anode chamber, the same material as the cathode chamber is used. Can be used. For example, nickel etc. can be mentioned. In addition, the anode coating is suitably a catalyst coating for oxygen generation. Examples of catalyst coatings include metals, oxides, hydroxides, and the like of platinum group metals and transition metals. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used.

Seventh Embodiment

Here, the 7th Embodiment of this invention is described in detail, referring FIGS. 112-122.

[Method of Manufacturing Electrolyzer]

The manufacturing method of the electrolytic cell which concerns on the 1st aspect (henceforth simply a "1st aspect") of 7th Embodiment (hereafter simply called "this embodiment" in the term of <7th Embodiment>) is a positive electrode. And an electrolytic electrode and a new diaphragm in an existing electrolytic cell having a negative electrode facing the positive electrode, a diaphragm fixed between the positive electrode and the negative electrode, and an electrolytic cell frame supporting the positive electrode, the negative electrode and the diaphragm. A method for manufacturing a new electrolytic cell by disposing a laminated body, the step (A) of releasing the fixing of the diaphragm in the electrolytic cell frame, and the diaphragm and the lamination after the step (A). It has a process (B) which exchanges a sieve.

As mentioned above, according to the manufacturing method of the electrolytic cell which concerns on a 1st aspect, an electrode can be updated without taking out each member outside the electrolytic cell frame, and the working efficiency at the time of electrode update in an electrolytic cell can be improved.

Moreover, the manufacturing method of the electrolytic cell which concerns on the 2nd aspect (henceforth simply a "2nd aspect") of this embodiment is a diaphragm fixed between an anode, a cathode which opposes the said anode, and the said anode and the said cathode. And disposing an electrode for electrolysis in an existing electrolytic cell having an electrolytic cell frame supporting the positive electrode, the negative electrode and the diaphragm, wherein the fixing of the diaphragm is performed in the electrolytic cell frame. And a step (B ') of disposing the electrolytic electrode between the diaphragm and the anode or the cathode after the step (A) of releasing and the step (A).

As mentioned above, also by the manufacturing method of the electrolytic cell which concerns on a 2nd aspect, an electrode can be updated without taking out each member outside the electrolytic cell frame, and the working efficiency at the time of electrode update in an electrolytic cell can be improved.

Hereinafter, when called "the manufacturing method of the electrolytic cell which concerns on this embodiment", it shall include the manufacturing method of the electrolytic cell which concerns on a 1st aspect, and the manufacturing method of the electrolytic cell which concerns on a 2nd aspect.

In the electrolytic cell manufacturing method according to the present embodiment, an existing electrolytic cell includes an anode, a cathode facing the anode, a diaphragm disposed between the anode and the cathode, an electrolytic cell supporting the anode, the cathode, and the membrane. It includes a frame as a constituent member. In other words, the existing electrolyzer includes a diaphragm, an electrolysis cell, and an electrolyzer frame which supports them. The existing electrolytic cell is not specifically limited as long as it contains the said structural member, Various well-known structures can be applied.

In the manufacturing method of the electrolytic cell which concerns on this embodiment, a new electrolytic cell is further equipped with the electrode or laminated body for electrolysis in addition to the member which already functions as an anode or a cathode in an existing electrolytic cell. That is, in the 1st aspect and 2nd aspect, the "electrode for electrode" arrange | positioned at the time of manufacture of a new electrolytic cell functions as an anode or a cathode, and is separate from the cathode and anode in an existing electrolytic cell. In the electrolytic cell manufacturing method according to the present embodiment, even if the electrolytic performance of the positive electrode and / or the negative electrode deteriorates due to the operation of the existing electrolytic cell, the performance of the positive electrode and / or the negative electrode is arranged by disposing the electrode for electrolysis separate from these. Can be updated. Further, in the first embodiment using the laminate, since the new ion exchange membranes are arranged together, the performance of the ion exchange membranes whose performance deteriorates with operation can be updated at the same time. The term "update performance" as used herein means that the performance is equal to the initial performance which the existing electrolytic cell had before being provided for operation, or the performance is higher than the initial performance.

In the manufacturing method of the electrolytic cell which concerns on this embodiment, the existing electrolytic cell assumes "the electrolytic cell already provided for operation", and the new electrolytic cell assumes the "electrolyzer not provided for operation yet". That is, once the electrolytic cell manufactured as a new electrolytic cell is provided to operation, it becomes "the existing electrolytic cell in this embodiment", and it is "the new electrolytic cell in this embodiment" which arrange | positioned the electrode or laminated body for this existing electrolytic cell. Becomes

EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of an electrolytic cell is explained in full detail, for example, when salt electrolysis is performed using an ion exchange membrane as a diaphragm. In addition, "electrolyzer in this embodiment" includes both "existing electrolyzer in this embodiment" and "new electrolyzer in this embodiment", unless specifically stated in the term of <seventh embodiment>. will be.

[Electrolysis cell]

First, the electrolytic cell which can be used as a structural unit of the electrolytic cell in this embodiment is demonstrated. 112 is a cross-sectional view of the electrolytic cell 1.

The electrolytic cell 1 includes the anode chamber 10, the cathode chamber 20, the partition wall 30 provided between the anode chamber 10 and the cathode chamber 20, and the anode provided in the anode chamber 10. 11 and a cathode 21 provided in the cathode chamber 20. If necessary, the base 18a and the reverse current absorbing layer 18b formed on the base 18a may be provided, and the reverse current absorber 18 provided in the cathode chamber may be provided. The positive electrode 11 and the negative electrode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 has the following cathode structure. The negative electrode structure 40 includes a negative electrode chamber 20, a negative electrode 21 provided in the negative electrode chamber 20, and a reverse current absorber 18 provided in the negative electrode chamber 20, and the reverse current absorber 18. 116 has the base material 18a and the reverse current absorption layer 18b formed on this base material 18a, and the cathode 21 and the reverse current absorption layer 18b are electrically connected. The negative electrode chamber 20 further includes a current collector 23, a support 24 supporting the current collector, and a metal elastic body 22. The metal elastic body 22 is provided between the electrical power collector 23 and the negative electrode 21. The support body 24 is provided between the collector 23 and the partition 30. The current collector 23 is electrically connected to the negative electrode 21 via the metal elastic body 22. The partition 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition 30, the support body 24, the collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorbing layer 18b are electrically connected to each other. The cathode 21 and the reverse current absorbing layer may be directly connected, or may be connected indirectly via a current collector, a support, a metal elastic body, a partition, or the like. It is preferable that the whole surface of the cathode 21 is covered with a catalyst layer for the reduction reaction. In addition, in the form of electrical connection, the partition 30 and the support body 24, the support body 24 and the collector 23, the collector 23 and the metal elastic body 22 are respectively directly attached, and the metal elastic body 22 ) May be laminated on the cathode 21. Welding etc. are mentioned as a method of attaching these structural members directly to each other. In addition, the reverse current absorber 18, the negative electrode 21, and the current collector 23 may be collectively referred to as the negative electrode structure 40.

FIG. 113 is a cross-sectional view of two electrolytic cells 1 adjacent in the electrolytic cell 4. 114 shows the electrolytic cell 4 as an existing electrolytic cell. FIG. 115 shows a step (different from steps (A) to (B) and steps (A ') to (B') for assembling the electrolytic cell 4.

As shown in FIG. 113, the electrolysis cell 1, the cation exchange membrane 2, and the electrolysis cell 1 are arranged in series in this order. The ion exchange membrane 2 is arrange | positioned between the anode chamber of one electrolytic cell 1 and the cathode chamber of the other electrolytic cell 1 among two electrolytic cells which adjoin in an electrolytic cell. In other words, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent thereto are spaced apart by the cation exchange membrane 2. As shown in FIG. 114, the electrolytic cell 4 is comprised in the form which supports the some electrolytic cell 1 connected in series via the ion exchange membrane 2 by the electrolytic cell frame 8. As shown in FIG. That is, the electrolytic cell 4 is equipped with the some electrolytic cell 1 arrange | positioned in series, the ion exchange membrane 2 arrange | positioned between the adjacent electrolytic cell 1, and the electrolyzer frame 8 which supports them. It is a bipolar electrolyzer. As shown in FIG. 115, the electrolytic cell 4 arrange | positions the some electrolysis cell 1 in series via the ion exchange membrane 2, and is connected by the press 5 in the electrolytic cell frame 8, Are assembled by The electrolytic cell frame is not particularly limited as long as it can support each member and can be connected, and various known forms can be applied. It does not specifically limit also as a means which connects each member with which an electrolytic cell frame is equipped, For example, what has a tie rod as a press means by a hydraulic pressure, or a mechanism is mentioned.

The electrolytic cell 4 has the positive terminal 7 and the negative terminal 6 connected to a power supply. The positive electrode 11 of the electrolytic cell 1 positioned at the shortest of the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4 is electrically connected to the positive electrode terminal 7. Among the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4, the negative electrode 21 of the electrolytic cell located at the end opposite to the positive electrode terminal 7 is electrically connected to the negative electrode terminal 6. The electric current at the time of electrolysis flows toward the negative electrode terminal 6 from the positive terminal 7 side via the positive electrode and the negative electrode of each electrolytic cell 1. Moreover, you may arrange | position the electrolytic cell (anode terminal cell) which has only an anode chamber, and the electrolytic cell (cathode terminal cell) which has only a cathode chamber in the both ends of the electrolytic cell 1 which connected. In this case, the positive terminal 7 is connected to the positive terminal cell disposed at one end thereof, and the negative terminal 6 is connected to the negative terminal cell arranged at the other end thereof.

In the case of electrolysis of brine, brine is supplied to each anode chamber 10, and pure or low concentration aqueous sodium hydroxide solution is supplied to the cathode chamber 20. Each liquid is supplied to each electrolytic cell 1 from electrolyte supply pipe (not shown) via electrolyte supply hose (not shown). In addition, electrolyte solution and the product by electrolysis are collect | recovered from an electrolyte collection pipe (not shown). In electrolysis, sodium ions in brine move from the anode chamber 10 of one electrolytic cell 1 through the ion exchange membrane 2 to the cathode chamber 20 of the neighboring electrolytic cell 1. Therefore, the current during electrolysis flows along the direction in which the electrolytic cells 1 are connected in series. That is, the current flows from the anode chamber 10 toward the cathode chamber 20 via the cation exchange membrane 2. By electrolysis of the brine, chlorine gas is produced on the anode 11 side, and sodium hydroxide (solute) and hydrogen gas are produced on the cathode 21 side.

(Positive room)

The anode chamber 10 includes a cathode 11 or an anode feeder 11. The term "feeder" as used herein means a deteriorated electrode (that is, an existing electrode), an electrode not coated with a catalyst, or the like. When the electrode for electrolysis in this embodiment is inserted in the anode side, 11 functions as a positive electrode feeder. When the electrode for electrolysis in this embodiment is not inserted in the anode side, 11 functions as an anode. In addition, the anode chamber 10 is disposed on an anode side electrolyte supply portion for supplying an electrolyte solution to the anode chamber 10 and an anode side electrolyte supply portion, and a baffle plate disposed to be substantially parallel or oblique with the partition wall 30. And it is preferable to have an anode side gas-liquid separation part arrange | positioned above the baffle plate and isolate | separates a gas from the electrolyte solution which gas mixed.

(anode)

When the electrode for electrolysis in this embodiment is not inserted in the anode side, the anode 11 is provided in the frame (namely, anode frame) of the anode chamber 10. As the anode 11, a metal electrode such as so-called DSA (registered trademark) can be used. DSA is a titanium-based electrode whose surface was covered with an oxide containing ruthenium, iridium and titanium.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Positive electrode feeder)

When the electrode for electrolysis in this embodiment is inserted in the anode side, the positive electrode feeder 11 is provided in the frame of the anode chamber 10. As the positive electrode feeder 11, a metal electrode such as DSA (registered trademark) or the like may be used, or titanium without a catalyst coating may be used. It is also possible to use DSA with a thinner catalyst coating thickness. Moreover, the used anode can also be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Anode-side electrolyte supply unit)

The anode-side electrolyte supply unit supplies the electrolyte solution to the anode chamber 10 and is connected to the electrolyte solution supply pipe. It is preferable that an anode side electrolyte supply part is arrange | positioned under the anode chamber 10. As an anode side electrolyte supply part, the pipe (dispersion pipe) etc. which have an opening part formed in the surface can be used, for example. It is more preferable that such a pipe is arrange | positioned in parallel with the bottom part 19 of an electrolysis cell along the surface of the anode 11. This pipe is connected to the electrolyte supply pipe (liquid supply nozzle) which supplies electrolyte solution in the electrolysis cell 1. The electrolyte solution supplied from the liquid supply nozzle is conveyed to the electrolysis cell 1 by the pipe, and is supplied to the inside of the anode chamber 10 from the opening provided in the surface of the pipe. By arranging the pipes parallel to the bottom portion 19 of the electrolytic cell along the surface of the anode 11, the electrolyte can be uniformly supplied into the anode chamber 10, which is preferable.

(Positive side gas-liquid separator)

It is preferable that the anode-side gas-liquid separator is disposed above the baffle plate. During electrolysis, the anode-side gas-liquid separator has a function of separating the generated gas such as chlorine gas and the electrolyte. In addition, unless otherwise indicated, an upper side means the upward direction in the electrolysis cell 1 of FIG. 112, and a lower side means the downward direction in the electrolysis cell 1 of FIG.

At the time of electrolysis, when the generated gas and electrolyte generated in the electrolytic cell 1 become mixed phase (gas-liquid mixed phase) and discharged out of the system, vibration occurs due to pressure fluctuation inside the electrolytic cell 1, and physical damage of the ion exchange membrane is prevented. I may cause it. In order to suppress this, it is preferable that the positive electrode side gas-liquid separation part for separating a gas and a liquid is provided in the electrolysis cell 1 of this embodiment. It is preferable that a defoaming plate for removing bubbles is provided in the anode-side gas-liquid separator. When a gas-liquid mixture flows through a vesicle plate, a bubble bursts and can be isolate | separated into electrolyte solution and gas. As a result, vibration during electrolysis can be prevented.

(Baffle version)

It is preferable that the baffle plate is disposed above the anode-side electrolyte supply portion, and is disposed substantially parallel to or inclined with the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. By providing the baffle plate, the electrolyte solution (salt water, etc.) can be circulated internally in the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged to be spaced apart from the space near the anode 11 and the space near the partition wall 30. From this viewpoint, the baffle plate is preferably provided so as to face each surface of the anode 11 and the partition wall 30. In the space near the anode partitioned by the baffle plate, electrolytic solution concentration (saline concentration) decreases as electrolysis proceeds, and product gas such as chlorine gas is generated. Thereby, the specific gravity difference of gas-liquid arises in the space near the anode 11 divided by the baffle plate, and the space near the partition 30. As shown in FIG. By using this, the internal circulation of the electrolyte solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolyte solution in the anode chamber 10 can be made more uniform.

Although not shown in FIG. 112, a current collector may be separately provided inside the positive electrode chamber 10. As such an electrical power collector, it can also be set as the material and structure similar to the electrical power collector of the negative electrode chamber mentioned later. In the anode chamber 10, the anode 11 itself can also function as a current collector.

(septum)

The partition 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition 30 may be called a separator and divides the anode chamber 10 and the cathode chamber 20. As the partition 30, a well-known thing can be used as a separator for electrolysis, For example, the partition which welded the plate which consists of nickel to the cathode side, and titanium to the anode side, etc. are mentioned.

(Cathode room)

The cathode chamber 20 functions as a cathode feeder when the electrode for electrolysis in the present embodiment is inserted on the cathode side, and when the electrode for electrolyte in the present embodiment is not inserted on the cathode side. , 21 functions as a cathode. When the reverse current absorber is provided, the negative electrode or the negative electrode feeder 21 and the reverse current absorber are electrically connected to each other. In addition, it is preferable that the cathode chamber 20 also has a cathode side electrolyte solution supply section and a cathode side gas-liquid separation section similarly to the anode chamber 10. In addition, description is abbreviate | omitted about the same thing as each part which comprises the anode chamber 10 among each site | part which comprises the cathode chamber 20. As shown in FIG.

(cathode)

When the electrode for electrolysis in this embodiment is not inserted in the cathode side, the cathode 21 is provided in the frame (namely, the cathode frame) of the cathode chamber 20. It is preferable that the negative electrode 21 has a catalyst layer which covers a nickel substrate and a nickel substrate. As a component of the catalyst layer on the nickel substrate, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd , Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho And metals such as Er, Tm, Yb and Lu, and oxides or hydroxides of the metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may give reduction process to the negative electrode 21 as needed. As the base material of the negative electrode 21, one in which nickel, nickel alloy, iron, or stainless steel is plated with nickel may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

(Cathode feeder)

When the electrode for electrolysis in this embodiment is inserted in the cathode side, the negative electrode feeder 21 is provided in the frame of the cathode chamber 20. The catalyst component may be coated on the negative electrode feeder 21. The catalyst component may be originally used as a negative electrode and remain. As components of the catalyst layer, Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Metals, such as Tm, Yb, Lu, and the oxide or hydroxide of this metal are mentioned. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / complex plating, CVD, PVD, pyrolysis, and thermal spraying. You may combine these methods. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may use what plated nickel with nickel, nickel alloys, iron, or stainless steel which are not catalyst coated. As the base material of the negative electrode feeder 21, a plated nickel on nickel, a nickel alloy, iron or stainless may be used.

As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used.

Reverse Current Absorption Layer

A material having a redox potential lower than the redox potential of the element for the catalyst layer of the cathode described above can be selected as the material of the reverse current absorbing layer. For example, nickel, iron, etc. are mentioned.

(Current collector)

The negative electrode chamber 20 preferably includes a current collector 23. This increases the current collecting effect. In the present embodiment, the current collector 23 is a porous plate, and is preferably disposed substantially parallel to the surface of the negative electrode 21.

The current collector 23 is preferably made of an electrically conductive metal such as nickel, iron, copper, silver, titanium, or the like. The current collector 23 may be a mixture of these metals, an alloy or a composite oxide. In addition, as long as it is a shape which functions as an electrical power collector, the shape of the electrical power collector 23 may be any shape, and plate-shaped or network-shaped may be sufficient as it.

(Metal elastomer)

By providing the metal elastic body 22 between the collector 23 and the cathode 21, each cathode 21 of the plurality of electrolytic cells 1 connected in series is pressed against the ion exchange membrane 2, The distance between each anode 11 and each cathode 21 can be shortened, and the voltage applied to the entire plurality of electrolytic cells 1 connected in series can be lowered. By lowering the voltage, the total consumption can be reduced. Moreover, when the metal elastic body 22 is provided and the laminated body containing the electrode for electrolysis in this embodiment is installed in an electrolytic cell, the said electrode for electrolysis by the pressure pressed by the metal elastic body 22 is carried out. Can be kept in a stable position.

As the metal elastic body 22, a spiral spring, a spring member such as a coil, a cushion mat, or the like can be used. As the metal elastic body 22, a suitable one can be appropriately adopted in consideration of a stress or the like which presses the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the collector 23 on the cathode chamber 20 side, or may be provided on the surface of the partition wall on the anode chamber 10 side. Usually, since both chambers are partitioned so that the cathode chamber 20 becomes smaller than the anode chamber 10, the metal elastic body 22 is connected to the current collector 23 of the cathode chamber 20 from the viewpoint of the strength of the frame body or the like. It is preferable to provide between the cathodes 21. Moreover, it is preferable that the metal elastic body 22 consists of metal which has electrical conductivity, such as nickel, iron, copper, silver, titanium.

(Support)

The negative electrode chamber 20 preferably includes a support 24 for electrically connecting the current collector 23 and the partition wall 30. Thereby, an electric current can flow efficiently.

The support 24 is preferably made of a metal having electrical conductivity such as nickel, iron, copper, silver, titanium, or the like. The shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod, plate, or network. The support body 24 is plate-shaped, for example. The plurality of supports 24 are disposed between the partition wall 30 and the current collector 23. The plurality of supports 24 are arranged such that their respective surfaces are parallel to each other. The support body 24 is disposed substantially perpendicular to the partition wall 30 and the current collector 23.

(Anode side gasket, cathode side gasket)

It is preferable that the anode side gasket is arranged on the surface of the frame body constituting the anode chamber 10. It is preferable that the cathode side gasket is arrange | positioned at the surface of the frame body which comprises the cathode chamber 20. As shown in FIG. The anode side gasket which one electrolytic cell has, and the cathode side gasket of the electrolysis cell adjacent to this are connected so that the electrolytic cells may be clamped (refer FIG. 113). By these gaskets, when connecting a plurality of electrolytic cells 1 in series via the ion exchange membrane 2, airtightness can be provided to a connection location.

A gasket seals between an ion exchange membrane and an electrolysis cell. As a specific example of a gasket, a frame-shaped rubber sheet etc. in which the opening part was formed in the center are mentioned. The gasket is required to be resistant to corrosive electrolytes, generated gases and the like and to be used for a long time. Therefore, from the viewpoint of chemical resistance and hardness, vulcanized products, peroxide crosslinked products and the like of ethylene propylene diene rubber (EPDM rubber) and ethylene propylene rubber (EPM rubber) are usually used as the gasket. Moreover, the gasket which coat | covered the area | region (contact part) which contact | connects a liquid as needed with fluororesin, such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether polymer (PFA), can also be used. These gaskets should just have opening parts, respectively, so that the flow of electrolyte solution may not be disturbed, The shape is not specifically limited. For example, a frame-shaped gasket is bonded with an adhesive or the like along the circumferential edge of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20. For example, when connecting two electrolytic cells 1 via the ion exchange membrane 2 (refer FIG. 113), when each electrolytic cell 1 which bonded the gasket through the ion exchange membrane 2 is fastened, do. Thereby, it can suppress that an electrolyte solution, the alkali metal hydroxide produced by electrolysis, chlorine gas, hydrogen gas, etc. leak to the exterior of the electrolysis cell 1.

[Laminated body]

In the electrolytic cell manufacturing method according to the present embodiment, the electrode for electrolysis can be used as a laminate with a diaphragm such as an ion exchange membrane or a microporous membrane. That is, the laminated body in this embodiment contains an electrode for electrolysis and a new diaphragm. The new diaphragm is not particularly limited as long as it is separate from the diaphragm in the existing electrolytic cell, and various known diaphragms can be applied. The new diaphragm may be the same as the diaphragm in the existing electrolytic cell in terms of material, shape, physical properties, and the like. Specific examples of the electrode for electrolysis and the diaphragm will be described later in detail.

(Step (A))

In the step (A) in the first aspect, the membrane is fixed in the electrolytic cell frame. The term "in the electrolytic cell frame" means that the step (A) is carried out while maintaining the state in which the electrolytic cell (that is, the member including the anode and the cathode) and the diaphragm are supported by the electrolytic cell frame. Excluding from is excluded. The method of releasing the fixing of the diaphragm is not particularly limited, but, for example, the pressing by the press machine in the electrolytic cell frame can be released, and a gap can be formed between the electrolytic cell and the diaphragm to take the diaphragm out of the electrolytic cell frame. The method of making it into a state, etc. are mentioned. In the step (A), it is preferable to release the fixing of the diaphragm in the electrolytic cell frame by sliding the anode and the cathode in the arrangement direction thereof, respectively. According to this operation, the diaphragm can be taken out of the electrolytic cell frame without taking out the electrolytic cell out of the electrolytic cell frame.

[Step (B)]

In process (B) in a 1st aspect, after a process (A), the diaphragm and laminated body in an existing electrolytic cell are exchanged. The method of exchange is not particularly limited, but for example, after the gap is formed between the electrolytic cell and the ion exchange membrane, an existing diaphragm to be updated is removed, and then a laminate is inserted into the gap. Can be mentioned. By this method, the laminate can be disposed on the surface of the anode or cathode in the existing electrolytic cell, and the performance of the ion exchange membrane, the anode and / or the cathode can be updated.

After performing step (B), it is preferable to fix the laminate in the electrolytic cell frame by pressing from the positive electrode and the negative electrode. Specifically, after the diaphragm and the laminated body in the existing electrolytic cell are replaced, each member in the existing electrolytic cell such as the laminated body and the electrolytic cell can be pressed again by a press. By this method, the laminate can be fixed on the surface of the positive electrode or the negative electrode in the existing electrolytic cell.

Based on FIG. 117A and 117B, the specific example of process (A)-(B) in a 1st aspect is demonstrated. First, the press by the press 5 is released, and the some electrolytic cell 1 and the ion exchange membrane 2 are made to slide in these arrangement directions (alpha). Thereby, the space | gap S can be formed between the electrolytic cell 1 and the ion exchange membrane 2, without taking out the electrolytic cell 1 out of the electrolytic cell frame 8, and the ion exchange membrane 2 Silver is in a state that can be taken out of the electrolytic cell frame 8. Subsequently, the ion exchange membrane 2 of the existing electrolytic cell to be replaced is taken out from the electrolytic cell frame 8, and instead, the new ion exchange membrane 2a and the laminate 9 of the electrolytic electrode 100 are adjacent to each other. It inserts between the cells 1 (namely, the space | gap S). In this way, the laminated body 9 is arrange | positioned between the adjacent electrolytic cells 1, and these are in the state supported by the electrolytic cell frame 8. As shown in FIG. Then, the some electrolysis cell 1 and the laminated body 9 are connected by pressing in the arrangement direction (alpha) by the press 5.

(Step (A '))

Also in the process (A ') in 2nd aspect, like a 1st aspect, fixation of a diaphragm is released in an electrolytic cell frame. Also in the step (A '), it is preferable to release the diaphragm in the electrolytic cell frame by sliding the anode and the cathode in the arrangement direction thereof, respectively. According to this operation, the diaphragm can be taken out of the electrolytic cell frame without taking out the electrolytic cell out of the electrolytic cell frame.

[Step (B ')]

In process (B ') in a 2nd aspect, after process (A'), an electrode for electrolysis is arrange | positioned between a diaphragm and an anode or a cathode. Although it does not specifically limit as a method of arrange | positioning an electrode for electrolysis, For example, the method of inserting an electrode for electrolysis into the said space after forming a space | gap between an electrolysis cell and an ion exchange membrane is mentioned. By this method, the electrolytic electrode can be disposed on the surface of the positive electrode or the negative electrode in the existing electrolytic cell, and the performance of the positive electrode or the negative electrode can be updated.

After performing step (B '), it is preferable to fix the electrode for electrolysis in the electrolytic cell frame by pressing from the positive electrode and the negative electrode. Specifically, after placing the electrolytic electrode on the surface of the positive electrode or the negative electrode in the existing electrolytic cell, each member in the existing electrolytic cell such as the electrolytic electrode and the electrolytic cell can be pressed again by a press. By this method, the laminate can be fixed on the surface of the positive electrode or the negative electrode in the existing electrolytic cell.

Based on FIG. 118A and 118B, the specific example of process (A ')-(B') in 2nd aspect is demonstrated. First, the press by the press 5 is released, and the some electrolytic cell 1 and the ion exchange membrane 2 are slid in these arrangement directions (alpha). Thereby, the space | gap S can be formed between the electrolytic cell 1 and the ion exchange membrane 2, without taking out the electrolytic cell 1 out of the electrolytic cell frame 8. Next, the electrode 100 for electrolysis is inserted between the adjacent electrolysis cells 1 (namely, the space | gap S). In this way, the electrode 100 for electrolysis is arrange | positioned between the adjacent electrolysis cells 1, and these are in the state supported by the electrolytic cell frame 8. As shown in FIG. Subsequently, the plurality of electrolytic cells 1 and the electrolytic electrodes 100 are connected by pressing in the array direction α by the press 5.

Moreover, in the process (B) in a 1st aspect, it is preferable to fix the said laminated body on at least one surface of an anode and a cathode under the temperature which a laminated body does not melt.

"The temperature at which a laminated body does not melt" can be specified as a softening point of a new diaphragm. Although the said temperature can vary with the material which comprises a diaphragm, it is preferable that it is 0-100 degreeC, It is more preferable that it is 5-80 degreeC, It is still more preferable that it is 10-50 degreeC.

Moreover, it is preferable that the said fixing is performed under normal pressure.

Moreover, after obtaining a laminated body by integrating an electrode for electrolysis and a new diaphragm under the temperature which the said diaphragm does not melt, it is preferable to use for a process (B).

As a specific method of the said integration, all the methods except the typical method of melting a diaphragm, such as thermocompression bonding, can be used, It does not specifically limit. As a preferable example, the method etc. which integrate with the surface tension of the said liquid through the liquid between the electrolytic electrode mentioned later and a diaphragm are mentioned.

[Electrode Electrode]

In the manufacturing method of the electrolytic cell which concerns on this embodiment, the electrode for electrolysis is not specifically limited as long as it can be used for electrolysis. The electrode for electrolysis may function as a cathode in an electrolytic cell, or may function as an anode. Moreover, regarding the material, shape, etc. of the electrode for electrolysis, an appropriate thing can be selected suitably in consideration of the structure of an electrolytic cell, etc. Hereinafter, although the preferable aspect of the electrode for electrolysis in this embodiment is demonstrated, these are only illustrations of the preferable aspect in the case of being integrated with a new diaphragm in a 1st aspect, and making it a laminated body, Electrolysis electrodes other than the aspect mentioned later It is also possible to appropriately employ.

The electrode for electrolysis in this embodiment can obtain favorable handling property, and is a unit from a viewpoint of having favorable adhesive force, such as a diaphragm, such as an ion exchange membrane and a microporous membrane, a feeder (a deteriorated electrode and a catalyst uncoated electrode), etc. The force applied per mass and unit area is preferably 1.6 N / (mg · cm 2) or less, more preferably less than 1.6 N / (mg · cm 2), still more preferably less than 1.5 N / (mg · cm 2) More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred.

From the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and even more preferably 0.1 N / mg · cm 2 or more. More preferably, it is 0.14 N / (mg * cm <2>) or more. 0.2 N / (mg * cm <2>) or more is more preferable from a viewpoint of the ease of handling in a large size (e.g., size 1.5 m x 2.5 m).

The said applied force can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, arithmetic mean surface roughness, etc., for example. More specifically, for example, when the porosity is increased, the applied force tends to be small, and when the porosity is decreased, the applied force tends to be large.

In addition, good handling properties can be obtained, good adhesion to diaphragms such as ion exchange membranes and microporous membranes, deteriorated electrodes, catalyst uncoated feeders and the like, and from the viewpoint of economy, the mass per unit area is 48 mg / cm 2 or less. It is preferable, More preferably, it is 30 mg / cm <2> or less, More preferably, it is 20 mg / cm <2> or less, It is preferable that it is 15 mg / cm <2> or less from a comprehensive viewpoint which combined handling property, adhesiveness, and economics. Although a lower limit is not specifically limited, For example, it is about 1 mg / cm <2>.

The said mass per unit area can be made into the said range by adjusting suitably the porosity mentioned later, thickness of an electrode, etc., for example. More specifically, for example, if the thickness is the same, the mass per unit area tends to be smaller when the porosity is increased, and the mass per unit area tends to be larger when the porosity is reduced.

The force applied can be measured by the following method (i) or (ii) and is as having described in the Example in detail. The force applied is also referred to as the value obtained by the measurement of the method (i) (also referred to as "the applied force 1"), and the value obtained by the measurement of the method (ii) (also referred to as the "force 2 applied"). ) May be the same or different, but any value is preferably less than 1.5 N / mg · cm 2.

[Method (i)]

Nickel plate obtained by blasting with alumina of particle number 320 (thickness 1.2 mm, width 200 mm) and an ion exchange membrane coated with inorganic particles and a binder on both sides of a membrane of a perfluorocarbon polymer into which an ion exchanger was introduced (horizontal 170 mm in length and the details of the ion-exchange membrane here, as described in the Example) and an electrode sample (130 mm in length) were laminated in this order, and this laminated body was fully immersed in pure water, and then laminated body. A sample for measurement is obtained by removing excess moisture adhering to the surface. In addition, the arithmetic mean surface roughness Ra of the nickel plate after a blasting process is 0.5-0.8 micrometer. The specific calculation method of arithmetic mean surface roughness Ra is as having described in the Example.

Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were raised in 10 mm in the vertical direction. Measure the weight when This measurement is performed three times to calculate an average value.

The average value is divided by the area of the overlapped portion of the electrode sample and the ion exchange membrane and the mass of the electrode sample of the overlapped portion with the ion exchange membrane, and the force applied per unit mass and unit area (1) (N / mg · cm 2) To calculate.

The force (1) applied per unit mass and unit area obtained by the method (i) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is preferable that it is 1.6 N / (mg * cm <2>) or less from a viewpoint of having more, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more and more preferably 0.14 N / (mg · cm 2) and 0.2 N / (mg · cm 2) from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m). ) Is more preferable.

[Method (ii)]

The nickel plate (thickness 1.2 mm, width 200 mm, the same nickel plate as the method (i)) and the electrode sample (length 130 mm) obtained by blasting with alumina of particle number 320 were laminated in this order. After fully immersing the laminate with pure water, a sample for measurement is obtained by removing excess moisture adhering to the laminate surface. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode samples in this measurement sample were raised at 10 mm / min in the vertical direction using a tensile compression tester, so that the electrode samples were 10 mm in the vertical direction. The weight at the time of rise is measured. This measurement is performed three times to calculate an average value.

This average value is divided by the area of the overlapped portion of the electrode sample and the nickel plate, and the mass of the electrode sample in the overlapped portion of the nickel plate, and the adhesive force 2 per unit mass and unit area (N / mg · cm 2) is obtained. Calculate.

The force (2) applied per unit mass and unit area obtained by the method (ii) can obtain good handling properties, and good adhesion to a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a catalyst-free feeder. It is preferable that it is 1.6 N / (mg * cm <2>) or less from a viewpoint of having more, More preferably, it is less than 1.6 N / (mg * cm <2>), More preferably, it is less than 1.5 N / (mg * cm <2>), More More preferably, it is 1.2 N / mg * cm <2> or less, More preferably, it is 1.20 N / mg * cm <2> or less. More preferably, it is 1.1 N / mg * cm <2> or less, More preferably, it is 1.10 N / mg * cm <2> or less, Especially preferably, it is 1.0 N / mg * cm <2> or less, It is 1.00 N / mg * cm <2> or less Particularly preferred. Further, from the viewpoint of further improving the electrolytic performance, the content is preferably more than 0.005 N / (mg · cm 2), more preferably 0.08 N / (mg · cm 2) or more, and still more preferably 0.1 N / (mg · Cm 2) or more, and even more preferably, from the viewpoint of ease of handling in a large size (eg, size 1.5 m × 2.5 m), still more preferably 0.14 N / (mg · cm 2) or more.

It is preferable that the electrolytic electrode in this embodiment contains an electrolytic electrode base material and a catalyst layer. Although the thickness (gauge thickness) of the said electrolytic electrode base material is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feedstock), and an electrode without a catalyst coating (grade 300 micrometers or less are preferable from a viewpoint of having a good adhesive force with the whole), and being rolled suitably, being able to bend it favorably, and facilitating handling in a large size (e.g., size 1.5 m x 2.5 m). 205 micrometers or less are more preferable, 155 micrometers or less are more preferable, 135 micrometers or less are still more preferable, 125 micrometers or less are still more preferable, 120 micrometers or less are still more preferable, 100 micrometers or less are further more preferable In addition, from a viewpoint of handling property and economical efficiency, 50 micrometers or less are further more preferable. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In the manufacturing method of the electrolytic cell which concerns on this embodiment, in integrating a new diaphragm and an electrode for electrolysis, it is preferable that a liquid is interposed between them. Any liquid may be used as long as the liquid generates surface tension such as water and an organic solvent. The greater the surface tension of the liquid, the greater the force exerted between the new diaphragm and the electrode for electrolysis. Therefore, a liquid having a large surface tension is preferable. Examples of the liquid include the following (the numerical values in parentheses indicate the surface tension of the liquid at 20 ° C).

Hexane (20.44 mN / m), Acetone (23.30 mN / m), Methanol (24.00 mN / m), Ethanol (24.05 mN / m), Ethylene glycol (50.21 mN / m), Water (72.76 mN / m)

If the liquid has a large surface tension, the new diaphragm and the electrode for electrolysis are integrated (to form a laminate), and the electrode update tends to be easier. The liquid between the new diaphragm and the electrode for electrolysis needs only to be such that the amount of liquid adheres to each other by the surface tension, and as a result, the amount of liquid is small. Therefore, even if it is mixed in the electrolyte after installation in the electrolytic cell of the laminate, the electrolysis itself is affected. Does not have

From a practical point of view, it is preferable to use the liquid whose surface tension is 24 mN / m-80 mN / m, such as ethanol, ethylene glycol, water, as a liquid. In particular, an aqueous solution obtained by dissolving caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like in water or alkali is preferable. In addition, surfactants may be included in these liquids to adjust the surface tension. By including surfactant, the adhesiveness of a new diaphragm and an electrode for electrolysis changes, and handling property can be adjusted. It does not specifically limit as surfactant, Both an ionic surfactant and a nonionic surfactant can be used.

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), From the viewpoint of having good adhesion, the ratio measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and also in a large size (e.g., size 1.5 m x 2.5 m). It is more preferable that it is 95% or more from the viewpoint of easy handling. The upper limit is 100%.

[Method (2)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the condition of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 280 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), It is preferable that it is 75% or more, and it is more preferable that it is 80% or more from the viewpoint of having favorable adhesive force, and being able to wind up in roll shape suitably, and bend | bending favorably. It is more preferable that it is 90% or more from a viewpoint that handling at a size (for example, size 1.5 m x 2.5 m) becomes easy. The upper limit is 100%.

[Method (3)]

An ion exchange membrane (170 mm long) and an electrode sample (130 mm long) are laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 145 mm) so that the electrode sample in the laminate is the outer side, and the laminate and the pipe are purely purified. It is sufficiently immersed and the excess water adhering to the laminate surface and the pipe is removed, and after 1 minute, the ratio (%) of the area of the portion where the ion exchange membrane (thickness 170 mm) and the electrode sample is in close contact is measured. .

Although the electrode for electrolysis in this embodiment is not specifically limited, favorable handling property can be obtained, diaphragm, such as an ion exchange membrane and a microporous membrane, a deteriorated electrode (feeder), and an electrode without a catalyst coating (feeder), It is preferable that it has a favorable adhesive force and is a porous structure from a viewpoint of the prevention of the residence of the gas which arises during electrolysis, and its porosity or porosity is 5 to 90% or less. The porosity is more preferably 10 to 80% or less, still more preferably 20 to 75%.

In addition, an opening ratio is a ratio of an opening part per unit volume. The calculation method varies depending on whether the opening is also considered to submicron order or only the visible opening. In this embodiment, the porosity A can be calculated by the following formula by calculating the volume V from the values of the gauge thickness, the width, and the length of the electrode, and by measuring the weight W.

A = (1- (W / (V × ρ)) × 100

ρ is the density (g / cm 3) of the material of the electrode. For example, 8.908 g / cm 3 for nickel and 4.506 g / cm 3 for titanium. The adjustment of the porosity is to change the area punching the metal per unit area if the punching metal, change the SW (short diameter), LW (long diameter), the feeding value if the expanded metal, the mesh diameter of the metal fiber, By changing the number of meshes, changing the pattern of the photoresist to be used for electroforming, changing the metal fiber diameter and fiber density for nonwoven fabrics, and changing the mold for forming the voids for the foamed metal, etc. I can adjust it.

Hereinafter, more specific embodiment of the electrode for electrolysis in this embodiment is demonstrated.

It is preferable that the electrolytic electrode which concerns on this embodiment contains an electrolytic electrode base material and a catalyst layer. The catalyst layer may be composed of a plurality of layers as described below or may have a single layer structure.

As shown in FIG. 119, the electrolytic electrode 100 which concerns on this embodiment is a pair of 1st layer 20 which coats both surfaces of the electrolytic electrode base material 10 and the electrolytic electrode base material 10. As shown in FIG. It is provided. It is preferable that the 1st layer 20 coat | covers the electrolytic electrode base material 10 whole. As a result, the catalytic activity and durability of the electrode for electrolysis tends to be improved. In addition, the first layer 20 may be laminated only on one surface of the electrode base 10 for electrolysis.

In addition, as shown in FIG. 119, the surface of the 1st layer 20 may be coat | covered with the 2nd layer 30. As shown in FIG. The second layer 30 preferably covers the entire first layer 20. In addition, only one surface of the first layer 20 may be laminated on the second layer 30.

(Electrode base for electrolysis)

The electrolytic electrode substrate 10 is not particularly limited, but a valve metal such as nickel, nickel alloy, stainless steel or titanium may be used, and at least one selected from nickel (Ni) and titanium (Ti) may be used. It is preferable to include the element of a species.

When stainless steel is used in a high concentration aqueous alkali solution, considering that iron and chromium are eluted, and that the electrical conductivity of stainless steel is about 1/10 of nickel, the electrolytic electrode substrate includes nickel (Ni). The substrate is preferred.

In addition, when the electrolytic electrode base material 10 is used in the chlorine gas generation | occurence atmosphere in the high concentration saline solution near saturation, it is preferable that a material is titanium with high corrosion resistance.

There is no restriction | limiting in particular in the shape of the electrode base material 10 for electrolysis, An appropriate shape can be selected according to the objective. As the shape, any of a punched metal, a nonwoven fabric, a foamed metal, an expanded metal, a metal porous foil formed by electroforming, and a so-called woven mesh produced by squeezing a metal wire can be used. Especially, a punching metal or an expanded metal is preferable. In addition, electroforming is a technique which manufactures a metal thin film of a precise pattern by combining photolithography and an electroplating method. It is a method of pattern-forming with a photoresist on a board | substrate, electroplating to the part which is not protected by a resist, and obtaining metal foil.

The shape of the electrode base material for electrolysis has suitable specifications depending on the distance between the anode and the cathode in the electrolytic cell. Although not particularly limited, in the case where the anode and the cathode have a finite distance, an expanded metal or a punched metal shape can be used, and in the case of a so-called zero gap electrolytic cell in which the ion exchange membrane and the electrode are in contact, a woven mesh woven with fine lines , Wire mesh, foamed metal, metal nonwoven fabric, expanded metal, punched metal, metal porous foil and the like can be used.

Examples of the electrode base 10 for electrolysis include a metal porous foil, a wire mesh, a metal nonwoven fabric, a punching metal, an expanded metal or a foamed metal.

As a board | plate material before processing with a punching metal and an expanded metal, the board | plate material roll-molded, electrolytic foil, etc. are preferable. It is preferable that the electrolytic foil is further plated with the same element as the base material as post-treatment to form irregularities on one or both surfaces.

In addition, it is preferable that the thickness of the electrolytic electrode base material 10 is 300 micrometers or less as mentioned above, It is more preferable that it is 205 micrometers or less, It is more preferable that it is 155 micrometers or less, It is further more preferable that it is 135 micrometers or less, 125 It is still more preferable that it is micrometer or less, It is still more preferable that it is 120 micrometers or less, It is still more preferable that it is 100 micrometers or less, It is further more preferable that it is 50 micrometers or less from a viewpoint of handling property and economy. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In the electrode base for electrolysis, it is preferable to relieve the residual stress at the time of processing by annealing the electrode base for electrolysis in an oxidizing atmosphere. Moreover, in order to improve the adhesiveness with the catalyst layer coat | covered with the said surface, the surface of an electrolytic electrode base material uses unevenness | corrugation using a steel grid, alumina powder, etc., and it is preferable to increase a surface area by acid treatment after that. Do. Or it is preferable to plating by the same element as a base material, and to increase a surface area.

In order to make the surface of the 1st layer 20 and the electrode base material 10 for electrolysis adhere to the electrode base material 10 for electrolysis, it is preferable to perform the process which increases a surface area. Examples of the treatment for increasing the surface area include a blast treatment using a cut wire, a steel grid, an alumina grid, and the like, an acid treatment using sulfuric acid or hydrochloric acid, a plating treatment using the same element as the substrate, and the like. Although arithmetic mean surface roughness Ra of the surface of a base material is not specifically limited, 0.05 micrometer-50 micrometers are preferable, 0.1-10 micrometers is more preferable, 0.1-8 micrometers is still more preferable.

Next, the case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

In FIG. 119, the 1st layer 20 which is a catalyst layer contains at least 1 sort (s) of oxide of ruthenium oxide, iridium oxide, and titanium oxide. Of ruthenium oxide RuO _2, etc., it may be mentioned. IrO ₂ etc. are mentioned as an iridium oxide. Examples of titanium oxides include TiO ₂ . The first layer 20 preferably contains two kinds of oxides of ruthenium oxide and titanium oxide, or three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide. Thereby, the 1st layer 20 becomes a more stable layer, and also adhesiveness with the 2nd layer 30 improves more.

In the case where the first layer 20 includes two kinds of oxides of ruthenium oxide and titanium oxide, titanium contained in the first layer 20 with respect to one mole of ruthenium oxide included in the first layer 20. It is preferable that it is 1-9 mol, and, as for an oxide, it is more preferable that it is 1-4 mol. By setting the composition ratio of the two kinds of oxides in this range, the electrolytic electrode 100 exhibits excellent durability.

When the first layer 20 includes three kinds of oxides of ruthenium oxide, iridium oxide and titanium oxide, the first layer 20 is included in the first layer 20 with respect to one mole of ruthenium oxide contained in the first layer 20. It is preferable that it is 0.2-3 mol, and, as for the iridium oxide used, it is more preferable that it is 0.3-2.5 mol. Moreover, it is preferable that it is 0.3-8 mol, and, as for 1 mol of titanium oxide contained in the 1st layer 20 with respect to 1 mol of ruthenium oxide contained in the 1st layer 20, it is more preferable. By making the composition ratio of three types of oxides into this range, the electrode 100 for electrolysis shows the outstanding durability.

When the 1st layer 20 contains at least 2 types of oxide chosen from a ruthenium oxide, an iridium oxide, and a titanium oxide, it is preferable that these oxides form a solid solution. By forming the oxide solid solution, the electrolytic electrode 100 exhibits excellent durability.

In addition to the above composition, as long as it contains at least one oxide of ruthenium oxide, iridium oxide and titanium oxide, those having various compositions can be used. For example, an oxide coating containing ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like, referred to as DSA (registered trademark), may be used as the first layer 20.

The first layer 20 does not need to be a single layer, but may include a plurality of layers. For example, the first layer 20 may include a layer containing three kinds of oxides and a layer containing two kinds of oxides. 0.05-10 micrometers is preferable and, as for the thickness of the 1st layer 20, 0.1-8 micrometers is more preferable.

(2nd floor)

It is preferable that the 2nd layer 30 contains ruthenium and titanium. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

It is preferable that the 2nd layer 30 contains palladium oxide, the solid solution of palladium oxide, and platinum, or the alloy of palladium and platinum. This makes it possible to further lower the chlorine overvoltage immediately after electrolysis.

The longer the longer the thickness of the second layer 30 can maintain the electrolytic performance, the thickness of the second layer 30 is preferably 0.05 to 3 m.

Next, the case where the electrode for electrolysis in this embodiment is used as a cathode for salt electrolysis is demonstrated.

(1st floor)

As a component of the first layer 20 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal include at least one kind, the alloy containing the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide and the platinum group metal is platinum, palladium, rhodium, It is preferable to contain at least 1 type of platinum group metal among ruthenium and iridium.

As a platinum group metal, it is preferable to contain platinum.

It is preferable that a platinum group metal oxide contains ruthenium oxide.

It is preferable that a platinum group metal hydroxide contains a ruthenium hydroxide.

As a platinum group metal alloy, it is preferable to include the alloy of platinum, nickel, iron, and cobalt.

Moreover, it is preferable to contain the oxide or hydroxide of a lanthanoid element as a 2nd component as needed. As a result, the electrolytic electrode 100 exhibits excellent durability.

The oxide or hydroxide of the lanthanoid-based element preferably contains at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium.

Moreover, it is preferable to contain the oxide or hydroxide of a transition metal as a 3rd component as needed.

By adding the third component, the electrolytic electrode 100 exhibits more excellent durability and can reduce the electrolytic voltage.

Examples of preferred combinations include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + platinum + palladium Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium + Sulfur, Ruthenium + Lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + samarium + cobalt, ruthenium + samarium + gallium, ruthenium + samarium + gallium, ruthenium + Samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + Nickel + palladium, bag Gold + nickel + ruthenium, an alloy of platinum and nickel, an alloy of platinum and cobalt, an alloy of platinum and iron, and the like.

When the platinum group metal, the platinum group metal oxide, the platinum group metal hydroxide, and the alloy containing the platinum group metal are not included, the main component of the catalyst is preferably nickel element.

It is preferable to contain at least 1 sort (s) among nickel metal, oxide, and hydroxide.

You may add a transition metal as a 2nd component. As a 2nd component to add, it is preferable to contain at least 1 type of element among titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon.

As a preferable combination, nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt, etc. are mentioned.

If necessary, an intermediate layer can be formed between the first layer 20 and the electrolytic electrode substrate 10. By providing the intermediate layer, the durability of the electrolytic electrode 100 can be improved.

As an intermediate | middle layer, what has affinity for both the 1st layer 20 and the electrode base material 10 for electrolysis is preferable. As the intermediate layer, nickel oxide, platinum group metal, platinum group metal oxide, and platinum group metal hydroxide are preferable. As an intermediate | middle layer, it can form by apply | coating and baking the solution containing the component which forms an intermediate | middle layer, and can also form a surface oxide layer by heat-processing a base material at 300-600 degreeC in air atmosphere. In addition, it can form by a well-known method, such as a thermal spraying method and an ion plating method.

(2nd floor)

As the components of the first layer 30 as the catalyst layer, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru , Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb And metals such as Dy, Ho, Er, Tm, Yb, Lu, and oxides or hydroxides of the metals.

At least 1 type of the alloy containing a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and a platinum group metal may be included, and does not need to be included. Examples of preferred combinations of the elements included in the second layer include combinations exemplified in the first layer. The combination of a 1st layer and a 2nd layer may be a combination with the same composition, and a composition ratio differs, and the combination of a different composition may be sufficient as it.

As thickness of a catalyst layer, the sum total of the formed catalyst layer and the intermediate | middle layer has preferable 0.01 micrometer-20 micrometers. If it is 0.01 micrometer or more, it can fully function as a catalyst. If it is 20 micrometers or less, a strong catalyst layer can be formed with little fall-out from a base material. 0.05 micrometers-15 micrometers are more preferable. More preferably, they are 0.1 micrometer-10 micrometers. More preferably, they are 0.2 micrometer-8 micrometers.

As thickness of an electrode, ie, the thickness of the sum total of an electrolytic electrode base material and a catalyst layer, 315 micrometers or less are preferable, 220 micrometers or less are more preferable, 170 micrometers or less are more preferable from a viewpoint of handling property of an electrode, 150 The thickness is even more preferable, 145 µm or less is particularly preferable, 140 µm or less is still more preferable, 138 µm or less is even more preferable, and 135 µm or less is even more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, it is preferable that it is 130 micrometers or less from a viewpoint similar to the above, More preferably, it is less than 130 micrometers, More preferably, it is 115 micrometers or less, More preferably, it is 65 micrometers or less. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, the thickness of an electrode can be calculated | required by measuring with a dejimatic thickness gauge (Mitsutoyo Corporation, minimum display 0.001 mm). The thickness of the electrode base material for electrodes is measured similarly to electrode thickness. The catalyst layer thickness can be obtained by subtracting the thickness of the electrode base material for electrolysis from the electrode thickness.

In the electrolytic cell manufacturing method according to the present embodiment, from the viewpoint of securing sufficient electrolytic performance, the electrode for electrolysis is Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni , Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La It is preferable to include at least one catalyst component selected from the group consisting of Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb and Dy.

In the present embodiment, the electrode for electrolysis can obtain better handling property as long as it is an electrode having a large elastic deformation region, and has better adhesion force such as a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, a catalyst-free feeder, and the like. From the viewpoint of having a thickness, the thickness of the electrode for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, still more preferably 170 µm or less, even more preferably 150 µm or less, and particularly 145 µm or less. Preferably, 140 micrometers or less are further more preferable, 138 micrometers or less are further more preferable, 135 micrometers or less are further more preferable. If it is 135 micrometers or less, favorable handling property can be obtained. Moreover, from a viewpoint similar to the above, 130 micrometers or less are preferable, less than 130 micrometers are more preferable, 115 micrometers or less are more preferable, and 65 micrometers or less are still more preferable. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In addition, in this embodiment, a "elastic deformation area | region is wide" means that it is difficult to produce the curvature resulting from winding after winding an electrode for electrolysis to make a winding body, and canceling a wound state. In addition, the thickness of an electrode for electrolysis means the thickness which combined the electrode base material for electrolysis and a catalyst layer, when including the catalyst layer mentioned later.

(Method for producing electrode for electrolysis)

Next, one Embodiment of the manufacturing method of the electrolytic electrode 100 is described in detail.

In the present embodiment, the first layer 20, preferably the second layer (on the electrode base material for electrolysis) is performed by a method such as baking (pyrolysis) of the coating film in an oxygen atmosphere or ion plating, plating, thermal spraying or the like. By forming 30), the electrode 100 for electrolysis can be manufactured. In this manufacturing method of the present embodiment, high productivity of the electrode 100 for electrolysis can be realized. Specifically, a catalyst layer is formed on the electrode base material for electrolysis by a coating step of applying a coating liquid containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing pyrolysis. Pyrolysis means here that the metal salt used as a precursor is heated and decomposed | disassembled into a metal or metal oxide and gaseous substance. Although decomposition products differ depending on the metal species used, the kind of salt, and the atmosphere in which pyrolysis is performed, most metals tend to form oxides in an oxidizing atmosphere. In the industrial production process of electrodes, pyrolysis is usually carried out in air, and in most cases metal oxides or metal hydroxides are formed.

(Formation of the first layer of the anode)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved at least 1 sort (s) of metal salt of ruthenium, iridium, and titanium to an electrolytic electrode base material, and thermally decomposes (baking) in presence of oxygen. The content of ruthenium, iridium and titanium in the first coating liquid is approximately the same as that of the first layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of the second layer)

The 2nd layer 30 is formed as needed, for example, apply | coating the solution containing a palladium compound and a platinum compound, or the solution (2nd coating liquid) containing a ruthenium compound and a titanium compound on the 1st layer 20 After that, it is obtained by pyrolysis in the presence of oxygen.

(Formation of First Layer of Cathode by Pyrolysis)

(Application process)

The 1st layer 20 is obtained by apply | coating the solution (1st coating liquid) which melt | dissolved the metal salt of various combinations to the electrode base material for electrolysis, and thermally decomposing (baking) in presence of oxygen. The content rate of the metal in a 1st coating liquid is substantially the same as the 1st layer 20.

The metal salt may be a chloride salt, nitrate, sulfate, metal alkoxide or any other form. Although the solvent of a 1st coating liquid can be selected according to the kind of metal salt, alcohol, such as water and butanol, etc. can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. Although the total metal concentration in the 1st coating liquid which melt | dissolved the metal salt is not specifically limited, The range of 10-150 g / L is preferable at the point of balance with the thickness of the coating film formed by one application | coating.

As a method of apply | coating a 1st coating liquid on the electrolytic electrode base material 10, the dip method which immerses the electrolytic electrode base material 10 in a 1st coating liquid, the method of brushing a 1st coating liquid, and 1st application | coating The roll method using the sponge roll impregnated with the liquid, the electrostatic coating method etc. which electrospray the electrolytic electrode base material 10 and a 1st coating liquid by opposing charge, and perform spray spraying are used. Especially, the roll method or electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)

After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it is made to dry at the temperature of 10-90 degreeC, and it thermally decomposes in the baking furnace heated to 350-650 degreeC. Between drying and pyrolysis, you may plasticize at 100-350 degreeC as needed. Drying, plasticity, and thermal decomposition temperature can be suitably selected according to the composition of a 1st coating liquid, and a solvent species. The longer the pyrolysis time per one is, the more preferable, but from the viewpoint of productivity of the electrode, 3 to 60 minutes are preferable, and 5 to 20 minutes are more preferable.

The coating, drying, and pyrolysis cycles are repeated to form a coating (first layer 20) to a predetermined thickness. After the 1st layer 20 is formed, if it bakes for a long time as needed and heats further, the stability of the 1st layer 20 can further be improved.

(Formation of intermediate layer)

An intermediate | middle layer is formed as needed, for example, is obtained by apply | coating the solution (2nd coating liquid) containing a palladium compound or a platinum compound on a base material, and then thermally decomposing in presence of oxygen. Alternatively, the nickel oxide intermediate layer may be formed on the surface of the substrate only by heating the substrate without applying the solution.

(Formation of First Layer of Cathode by Ion Plating)

The first layer 20 may be formed by ion plating.

As an example, the method of fixing a base material in a chamber, and irradiating an electron beam to a metal ruthenium target is mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and ruthenium is deposited on the substrate as ruthenium oxide.

(Formation of First Layer of Cathode by Plating)

The first layer 20 can also be formed by a plating method.

As an example, when a base material is used as a cathode and electrolytic plating is performed in the electrolyte solution containing nickel and tin, alloy plating of nickel and tin can be formed.

(Formation of First Layer of Cathode by Thermal Spray)

The first layer 20 can also be formed by thermal spraying.

As an example, by spraying nickel oxide particles on a substrate, a catalyst layer in which metal nickel and nickel oxide are mixed can be formed.

Hereinafter, the ion exchange membrane which concerns on one aspect of a diaphragm is explained in full detail.

[Ion exchange membrane]

The ion exchange membrane is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various ion exchange membranes can be applied. In the manufacturing method of the electrolytic cell which concerns on this embodiment, it is preferable to use the membrane main body containing the hydrocarbon type polymer or fluorine-containing polymer which has an ion exchange group, and the ion exchange membrane which has a coating layer formed on at least one surface of this membrane main body. In addition, it is preferable that the coating layer contains inorganic particles and a binder, and the specific surface area of the coating layer is 0.1-10 m 2 / g. The ion-exchange membrane of such a structure has little influence on the electrolytic performance by the gas which generate | occur | produces during electrolysis, and it tends to exhibit stable electrolytic performance.

The membrane of the perfluorocarbon polymer into which the ion exchange group is introduced is a sulfonic acid layer having an ion exchange group derived from a sulfo group (group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and an ion exchange group derived from a carboxyl group. It is provided with either a carboxylic sancheung having a - (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). In view of strength and dimensional stability, it is preferable to further have a reinforcing core material.

The inorganic particles and the binder will be described in detail in the description section of the coating layer below.

It is a cross-sectional schematic diagram which shows one Embodiment of an ion exchange membrane. The ion exchange membrane 1 has a membrane main body 10 containing a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group, and coating layers 11a and 11b formed on both surfaces of the membrane main body 10.

In the ion exchange membrane 1, the membrane main body 10 is a sulfonic acid layer 3 having an ion exchange group derived from a sulfo group (a group represented by -SO _3- , hereinafter also referred to as a "sulfonic acid group"), and ions derived from a carboxyl group. exchanger has a strength and dimensional stability are enhanced by the carboxylic sancheung 2 provided, and the reinforcement core (4) having a (-CO ₂ also called a group, hereinafter "carboxylic acid group" represented by). Since the ion exchange membrane 1 is provided with the sulfonic acid layer 3 and the carboxylic acid layer 2, it is suitably used as a cation exchange membrane.

In addition, the ion exchange membrane may have only one of a sulfonic acid layer and a carboxylic acid layer. In addition, the ion exchange membrane does not necessarily need to be reinforced by the reinforcing core, and the arrangement state of the reinforcing core is not limited to the example of FIG. 120.

(The membrane body)

First, the membrane main body 10 constituting the ion exchange membrane 1 will be described.

The membrane main body 10 may have a function of selectively permeating cations, and may include a hydrocarbon-based polymer or a fluorine-containing polymer having an ion exchange group. The structure and the material thereof are not particularly limited, and a suitable one can be appropriately selected. have.

The hydrocarbon-based polymer or fluorine-containing polymer having an ion exchange group in the membrane main body 10 can be obtained from a hydrocarbon-based polymer or a fluorine-containing polymer having an ion-exchange precursor which can be an ion-exchange group, for example, by hydrolysis or the like. Specifically, for example, the main chain is made of a fluorinated hydrocarbon, and has a group (ion exchanger precursor) which can be converted into an ion exchanger by hydrolysis or the like as a pendant side chain, and also a polymer which can be melt processed (hereinafter referred to as "fluorine-containing polymer). (a) ") to produce the precursor of the membrane main body 10, and then convert the ion exchanger precursor into the ion exchanger to obtain the membrane main body 10.

The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the third group below. have. Moreover, it can also manufacture by the homopolymerization of 1 type of monomers chosen from any of the following 1st group, the following 2nd group, and the following 3rd group.

As a monomer of a 1st group, a vinyl fluoride compound is mentioned, for example. Examples of the vinyl fluoride compound include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and the like. In particular, when the ion exchange membrane is used as the alkali electrolytic membrane, the vinyl fluoride compound is preferably a perfluoro monomer, and is perfluoro selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. Monomer is preferred.

As a monomer of a 2nd group, the vinyl compound which has a functional group which can be converted into a carboxylic acid type ion exchange group (carboxylic acid group) is mentioned, for example. Of a vinyl compound having a functional group that can be converted to a carboxylic acid group, for example, and the like can be _{CF 2 = CF (OCF 2 CYF} ) s -O (CZF) t monomers represented by -COOR (wherein, s is 0 An integer of -2, t represents an integer of 1 to 12, Y and Z each independently represents F or CF ₃ , and R represents a lower alkyl group, for example, a lower alkyl group is an alkyl group having 1 to 3 carbon atoms. .).

Among these, CF is _{2 = CF (OCF 2 CYF)} n -O (CF 2) _m -COOR compound represented by are preferred. Here n represents an integer of 0 to 2, m represents an integer of 1 to 4, Y represents F or CF ₃ , and R represents CH ₃ , C ₂ H ₅ or C ₃ H ₇ .

When the ion exchange membrane is used as a cation exchange membrane for alkali electrolysis, it is preferable to use at least a perfluoro compound as the monomer. However, since the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis, the alkyl group ( R) may not be a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

As a monomer of a 2nd group, the monomer shown below is more preferable among the above.

CF ₂ = CFOCF ₂ -CF (CF ₃ ) OCF ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CF [OCF ₂ -CF (CF ₃ )] ₂ O (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₂ COOCH ₃ ,

CF ₂ = CFO (CF ₂ ) ₃ COOCH ₃ .

As a monomer of a 3rd group, the vinyl compound which has a functional group which can be converted into a sulfone type ion exchange group (sulfonic acid group) is mentioned, for example. A vinyl compound having a functional group that can be converted into a sulfonic acid is, for example, CF ₂ = a monomer represented by the _{CFO-X-CF 2 -SO 2} F are preferred (wherein, X represents an alkylene group of a perfluoroalkyl.). As these specific examples, the monomer etc. which are shown below are mentioned.

CF ₂ = CFOCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CF (CF ₂ ) ₂ SO ₂ F,

CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] ₂ CF ₂ CF ₂ SO ₂ F,

CF ₂ = CFOCF ₂ CF (CF ₂ OCF ₃ ) OCF ₂ CF ₂ SO ₂ F.

Among these, CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F are more preferable.

The copolymer obtained from these monomers can be manufactured by the polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, especially the general polymerization method used with respect to tetrafluoroethylene. For example, in the non-aqueous method, inert solvents such as perfluorohydrocarbon and chlorofluorocarbon are used, and in the presence of radical polymerization initiators such as perfluorocarbon peroxide and azo compound, the temperature is 0 to 200 캜 and the pressure is 0.1 to 0.1. The polymerization reaction can be carried out under the condition of 20 MPa.

In the said copolymerization, the kind and ratio of the combination of the said monomers are not specifically limited, It selects according to the kind and quantity of the functional group to provide to the fluorine-containing polymer obtained. For example, in the case of using a fluorine-containing polymer containing only a carboxylic acid group, at least one monomer may be selected and copolymerized from the first group and the second group, respectively. In the case of using a fluorine-containing polymer containing only a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group and the third group, respectively. In the case of using a fluorine-containing polymer having a carboxylic acid group and a sulfonic acid group, at least one monomer may be selected and copolymerized from the monomers of the first group, the second group, and the third group, respectively. In this case, the target fluorine-containing polymer can also be obtained by separately polymerizing the copolymer composed of the first group and the second group and the copolymer composed of the first group and the third group, and then mixing the copolymer separately. . Moreover, although the mixing ratio of each monomer is not specifically limited, When increasing the quantity of functional groups per unit polymer, what is necessary is just to increase the ratio of the monomer chosen from the said 2nd group and the 3rd group.

Although the total ion exchange capacity of a fluorine-containing copolymer is not specifically limited, It is preferable that it is 0.5-2.0 mg equivalent / g, and it is more preferable that it is 0.6-1.5 mg equivalent / g. Here, total ion exchange capacity means the equivalent of the exchanger per unit weight of dry resin, and can be measured by neutralization titration etc.

In the membrane main body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorine-containing polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorine-containing polymer having a carboxylic acid group are laminated. . By using this layer structure as the membrane main body 10, the selective permeability of cations such as sodium ions can be further improved.

In the case where the ion exchange membrane 1 is disposed in the electrolytic cell, the sulfonic acid layer 3 is usually disposed on the anode side of the electrolytic cell and the carboxylic acid layer 2 on the cathode side of the electrolytic cell.

It is preferable that the sulfonic acid layer 3 is comprised from the material with low electrical resistance, and it is preferable that a film thickness is thicker than the carboxylic acid layer 2 from a viewpoint of film strength. The film thickness of the sulfonic acid layer 3 becomes like this. Preferably it is 2-25 times of the carboxylic acid layer 2, More preferably, it is 3-15 times.

It is preferable that the carboxylic acid layer 2 has high anion exclusion property even if it is thin. Anion-exclusion here means the property which wants to interrupt the invasion and permeation | transmission of anion to the ion exchange membrane 1. In order to improve anion exclusion, disposing a carboxylic acid layer having a small ion exchange capacity with respect to the sulfonic acid layer is effective.

As the fluorine-containing polymer used for the sulfonic acid layer 3, for example, a polymer obtained by using CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F as the third group of monomers is suitable.

Carboxylic acids referred to as the fluorine-based polymer for use in sancheung (2) is, for example, as monomers of group 2 _{CF 2 = CFOCF 2 CF (CF} 2) O (CF 2) a polymer obtained by using ₂ COOCH ₃ are suitable.

(Coating layer)

It is preferable that an ion exchange membrane has a coating layer on at least one surface of a membrane main body. As shown in FIG. 120, in the ion exchange membrane 1, the coating layers 11a and 11b are formed on both surfaces of the membrane body 10, respectively.

The coating layer includes inorganic particles and a binder.

As for the average particle diameter of an inorganic particle, it is more preferable that it is 0.90 micrometer or more. If the average particle diameter of the inorganic particles is 0.90 µm or more, the durability against impurities as well as gas adhesion is greatly improved. In other words, a particularly significant effect is obtained by increasing the average particle diameter of the inorganic particles and by satisfying the above-described specific surface area. In order to satisfy such an average particle diameter and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by crushing gemstones can be used. Preferably, the inorganic particles obtained by gemstone grinding can be suitably used.

In addition, the average particle diameter of an inorganic particle can be 2 micrometers or less. If the average particle diameter of an inorganic particle is 2 micrometers or less, it can prevent that a film | membrane is damaged by an inorganic particle. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 µm.

Here, an average particle diameter can be measured with a particle size distribution meter ("SALD2200" Shimadzu Corporation).

It is preferable that the shape of an inorganic particle is an irregular shape. Resistance to impurities is further improved. In addition, the particle size distribution of the inorganic particles is preferably wide.

It is preferable that an inorganic particle contains at least 1 sort (s) of inorganic substance chosen from the group which consists of an oxide of a group IV element of a periodic table, a nitride of a group IV element of a periodic table, and a carbide of a group IV element of a periodic table. More preferably, they are particles of zirconium oxide from the viewpoint of durability.

It is preferable that this inorganic particle is an inorganic particle manufactured by crushing the gemstone of an inorganic particle, or it is preferable to make spherical particle | grains of the uniform diameter of particle | grains into an inorganic particle by melting and refine | purifying the gemstone of an inorganic particle.

Examples of the raw material grinding method include, but are not particularly limited to, ball mills, bead mills, colloid mills, conical mills, disc mills, edge mills, milling mills, hammer mills, pellet mills, VSI mills, willy mills, roller mills, and jet mills. Etc. can be mentioned. Moreover, it is preferable to wash | clean after grinding | pulverization, and it is preferable to be acid-processed at that time. As a result, impurities such as iron adhering to the surface of the inorganic particles can be reduced.

The coating layer preferably comprises a binder. A binder is a component which keeps inorganic particle on the surface of an ion exchange membrane, and comprises a coating layer. It is preferable that a binder contains a fluorine-containing polymer from a viewpoint of resistance to electrolyte solution or the product by electrolysis.

As a binder, it is more preferable that it is a fluorine-containing polymer which has a carboxylic acid group or a sulfonic acid group from a tolerance with respect to the electrolyte solution and the product by electrolysis, and adhesiveness to the surface of an ion exchange membrane. When forming a coating layer on the layer (sulfonic acid layer) containing a fluorine-containing polymer which has a sulfonic acid group, it is more preferable to use the fluorine-containing polymer which has a sulfonic acid group as a binder of this coating layer. Moreover, when forming a coating layer on the layer (carboxylic acid layer) containing the fluorine-containing polymer which has a carboxylic acid group, it is more preferable to use the fluorine-containing polymer which has a carboxylic acid group as a binder of this coating layer.

It is preferable that it is 40-90 mass%, and, as for content of an inorganic particle in a coating layer, it is more preferable that it is 50-90 mass%. Moreover, it is preferable that it is 10-60 mass%, and, as for content of a binder, it is more preferable that it is 10-50 mass%.

The distribution density of the coating layer in the ion exchange membrane is preferably 0.05 to 2 mg per cm 2. In addition, when an ion exchange membrane has a concave-convex shape on the surface, it is preferable that the distribution density of a coating layer is 0.5-2 mg per cm <2>.

It does not specifically limit as a method of forming a coating layer, A well-known method can be used. For example, the method of apply | coating the coating liquid which disperse | distributed inorganic particle to the solution containing a binder by spray etc. is mentioned.

(Reinforced heartwood)

It is preferable that the ion exchange membrane has a reinforcing core material disposed inside the membrane body.

The reinforcing core is a member for enhancing the strength and dimensional stability of the ion exchange membrane. By arrange | positioning a reinforcing core material inside a membrane main body, especially expansion and contraction of an ion exchange membrane can be controlled to a desired range. Such an ion exchange membrane can maintain excellent dimensional stability for a long time without being stretched more than necessary in electrolysis or the like.

The configuration of the reinforcing core is not particularly limited, and may be formed by spinning a yarn called reinforcing yarn, for example. The reinforcement yarn mentioned here is a member which constitutes a reinforcing core material, which can impart desired dimensional stability and mechanical strength to the ion exchange membrane, and refers to a yarn that can stably exist in the ion exchange membrane. By using the reinforcing core material which radiated such reinforcement yarn, further excellent dimensional stability and mechanical strength can be provided to the ion exchange membrane.

The material of the reinforcing core material and the reinforcing yarn used for this is not particularly limited, but it is preferable that the material is resistant to acids, alkalis, or the like. desirable.

Examples of the fluorine-containing polymer used in the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether polymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), tetra Fluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, vinylidene fluoride polymer (PVDF), and the like. Among these, it is preferable to use the fiber which consists of polytetrafluoroethylene from a heat resistant and chemical resistant viewpoint especially.

The diameter of the reinforcing sand used for the reinforcing core is not particularly limited, but is preferably 20 to 300 denier, and more preferably 50 to 250 denier. The weave density (number of insertion lines per unit length) is preferably 5 to 50 lines / inch. The form of the reinforcing core is not particularly limited, and for example, a woven fabric, a nonwoven fabric, a knitted fabric, or the like is used, but it is preferably a form of a woven fabric. In addition, the thickness of the woven fabric is preferably 30 to 250 m, more preferably 30 to 150 m.

As the woven fabric or knitted fabric, monofilament, multifilament or yarns, slit yarns, and the like thereof can be used, and the weaving method can use various weaving methods such as plain weave, leno weave, knitting, cord weave, and seerker.

The weaving method and arrangement of the reinforcing core material in the membrane main body are not particularly limited and can be appropriately arranged in consideration of the size and shape of the ion exchange membrane, the desired physical properties and the use environment for the ion exchange membrane, and the like.

For example, the reinforcing core may be disposed along a predetermined direction of the membrane body, but from the viewpoint of dimensional stability, the reinforcing core is disposed along the predetermined first direction, and a second direction substantially perpendicular to the first direction is provided. Therefore, it is preferable to arrange a separate reinforcing core material. By arranging the plurality of reinforcing cores so as to run substantially straight inside the longitudinal membrane body of the membrane body, further superior dimensional stability and mechanical strength can be imparted in multiple directions. For example, an arrangement for weaving the reinforcing core material (warp) disposed along the longitudinal direction and the reinforcing core material (weft) arranged along the transverse direction on the surface of the membrane body is preferable. Lion weaved by inserting the same number of wefts into the weaving plain weave by twisting and inserting warp and weft alternately, or by weaving two warp and leno weaving by twisting two warp and two or several lines. It is more preferable to use a woven fabric (a loom) from the viewpoint of dimensional stability, mechanical strength, and ease of manufacture.

In particular, it is preferable that the reinforcing core is disposed along both directions of the MD direction (Machine Direction direction) and the TD direction (Transverse Direction direction) of the ion exchange membrane. That is, it is preferable to be woven in the MD direction and the TD direction. Here, MD direction means the direction (flow direction) in which a membrane main body and various core materials (for example, a reinforced core material, a reinforcement yarn, a sacrificial yarn etc. mentioned later) are conveyed in the manufacturing process of the ion exchange membrane mentioned later, and a TD direction is It refers to a direction approximately perpendicular to the MD direction. The yarn woven along the MD direction is called MD yarn, and the yarn woven along the TD direction is called TD yarn. Usually, the ion exchange membrane used for electrolysis is rectangular, and a longitudinal direction becomes MD direction, and the width direction becomes a TD direction in many cases. By weaving the reinforced MD core material and the reinforced TD core material, it is possible to give even more excellent dimensional stability and mechanical strength in multiple directions.

The spacing of the reinforcing cores is not particularly limited and can be appropriately arranged in consideration of desired physical properties, use environment, and the like for the ion exchange membrane.

The opening ratio of the reinforcing core material is not particularly limited, and is preferably 30% or more, more preferably 50% or more and 90% or less. The opening ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane.

The opening ratio of the reinforcing core is the total area (B) of the surface through which substances such as ions (electrolyte and cation (for example, sodium ions) contained) in the area (A) of either surface of the membrane body can pass. The ratio of (B / A). The total area (B) of the surface through which substances such as ions can pass can be referred to as the total area of the region where cations, electrolytes, and the like are not blocked by the reinforcing core included in the ion exchange membrane.

It is a schematic diagram for demonstrating the opening ratio of the reinforcing core material which comprises an ion exchange membrane. 121 enlarges a part of the ion exchange membrane and shows only the arrangement of the reinforcing core materials 21 and 22 in the region, and the illustration of other members is omitted.

The total area C of the reinforcement core from the area A of the region including the area of the reinforcement core, which is also surrounded by the reinforcement core 21 arranged in the longitudinal direction and the reinforcement core 22 arranged in the horizontal direction. By subtracting, the total area B of the area through which substances such as ions in the area A of the area can pass can be obtained. That is, an opening ratio can be calculated | required by following formula (I).

Aperture ratio = (B) / (A) = ((A)-(C)) / (A). (I)

Among the reinforcing cores, a particularly preferable form is a tape yarn or a highly oriented monofilament containing PTFE in view of chemical resistance and heat resistance. Specifically, a high-strength porous sheet made of PTFE is a tape yarn slitted in tape form, or a 50 to 300 denier of a highly oriented monofilament made of PTFE, and a woven density of 10 to 50 lines / inch. It is more preferable that it is a reinforcement core material whose thickness is the range of 50-100 micrometers. It is more preferable that the opening ratio of the ion exchange membrane including such a reinforcing core material is 60% or more.

Examples of the shape of the reinforcing yarn include round yarns and tape-like yarns.

(Communication hole)

It is preferable that the ion exchange membrane has a communication hole inside the membrane main body.

The communication hole refers to a hole that can be a flow path for ions or electrolyte generated during electrolysis. In addition, a communication hole is a tubular hole formed in the inside of a membrane main body, and is formed by eluting the sacrificial core material (or sacrificial thread) mentioned later. The shape and diameter of the communication hole can be controlled by selecting the shape and diameter of the sacrificial core material (sacrificial yarn).

By forming communication holes in the ion exchange membrane, the mobility of the electrolyte can be ensured at the time of electrolysis. Although the shape of a communication hole is not specifically limited, According to the manufacturing method mentioned later, it can be set as the shape of the sacrificial core material used for formation of a communication hole.

The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. With such a structure, in the part where the communication hole is formed in the cathode side of the reinforcing core material, ions (for example, sodium ions) transported through the electrolyte solution filled in the communication hole can also flow to the cathode side of the reinforcing core material. As a result, since the flow of cation is not blocked, the electrical resistance of the ion exchange membrane can be made lower.

The communication hole may be formed along only one predetermined direction of the membrane main body constituting the ion exchange membrane, but is formed in both the longitudinal direction and the transverse direction of the membrane main body in view of exhibiting more stable electrolytic performance. desirable.

[Production method]

As a suitable manufacturing method of an ion exchange membrane, the method of having the following (1) process-(6) process is mentioned.

(1) Process: The process of manufacturing the fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(2) Process: If necessary, a sacrificial yarn is disposed between adjacent reinforcing cores by at least weaving a plurality of reinforcing cores and a property of dissolving in an acid or alkali and forming at least a communication hole. To obtain the finished reinforcement.

(3) Process: The process of film-forming the said fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.

(4) Step: The step of embedding the reinforcing material in the film as necessary to obtain a membrane body having the reinforcing material disposed therein.

(5) Process: The process (hydrolysis process) of hydrolyzing the membrane main body obtained at process (4).

(6) Process: The process (coating process) of forming a coating layer in the film main body obtained at the process (5).

Hereinafter, each process is explained in full detail.

(1) Process: process for producing fluorine-containing polymer

In the step (1), the fluorine-containing polymer is produced by using the monomers of the raw materials described in the first group to the third group. In order to control the ion exchange capacity of a fluorine-containing polymer, in the manufacture of the fluorine-containing polymer which forms each layer, the mixing ratio of the monomer of a raw material may be adjusted.

(2) Process: manufacturing process of reinforcement

A reinforcing material is a woven fabric etc. which woven the reinforcement yarn. The reinforcing material is embedded in the film to form the reinforcing core material. When using an ion exchange membrane having communication holes, the sacrificial yarn is also woven into the reinforcing material. In this case, the blending amount of the sacrificial material is preferably 10 to 80 mass%, more preferably 30 to 70 mass% of the entire reinforcing material. By weaving a sacrificial thread, the mesh shift | offset of a reinforcement core material can also be prevented.

The sacrificial material has solubility in a film production process or an electrolytic environment, and rayon, polyethylene terephthalate (PET), cellulose, polyamide, and the like are used. Moreover, polyvinyl alcohol etc. which have a thickness of 20-50 denier and consist of monofilament or multifilament are also preferable.

In the step (2), by adjusting the arrangement of the reinforcing core material or the sacrificial material, the opening ratio, the arrangement of the communication holes, and the like can be controlled.

(3) process: filming process

In the step (3), the fluorine-containing polymer obtained in the step (1) is filmed using an extruder. A single layer structure may be sufficient as a film, and as above-mentioned, the two-layered structure of a sulfonic acid layer and a carboxylic acid layer may be sufficient, and the multilayered structure of three or more layers may be sufficient as it.

As a method of film-forming, the following are mentioned, for example.

A method of filming each of the fluorine-containing polymer having a carboxylic acid group and the fluorine-containing polymer having a sulfonic acid group separately.

A method in which a fluorine-containing polymer having a carboxylic acid group and a fluorine-containing polymer having a sulfonic acid group are co-extruded into a composite film.

In addition, a plurality of films may be sufficient respectively. Moreover, coextrusion of different kinds of films is preferable because it contributes to raising the adhesive strength of an interface.

(4) step: the step of obtaining the membrane body

In the step (4), the film body in which the reinforcing material is embedded is obtained by embedding the reinforcing material obtained in the step (2) inside the film obtained in the step (3).

As a preferable formation method of a film main body, (i) the fluorine-containing polymer which has a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) located in the cathode side (henceforth, the layer which consists of this is called a 1st layer), And forming a fluorine-containing polymer having a sulfonic acid group precursor (e.g., a sulfonylfluoride functional group) (hereinafter, referred to as a second layer) by a coextrusion method, and heating and vacuum source as necessary. Is laminated on a flat plate or drum having a large number of pores on the surface of the reinforcing material and the second layer / first layer composite film in the order of a reinforcing material and a heat-resistant release paper having air permeability. Integrating while removing air between each layer by decompression under temperature; (ii) Apart from the second layer / first layer composite film, the fluorine-containing polymer (third layer) having a sulfonic acid group precursor is previously filmed alone, and the surface is heated and heated using a vacuum source if necessary. The laminated film was laminated in the order of a composite film consisting of a third layer film, a reinforcing core material, and a second layer / first layer via a heat-resistant release paper having air permeability on a flat plate or a drum having a large number of pores thereon. The method of integrating, removing the air between each layer by pressure reduction under the temperature which melt | dissolves is mentioned.

Here, coextrusion of a 1st layer and a 2nd layer contributes to raising the adhesive strength of an interface.

Moreover, the method of integrating under reduced pressure has the feature that the thickness of the 3rd layer on a reinforcement material becomes large compared with the pressure press method. In addition, since the reinforcing material is fixed to the inner surface of the membrane main body, it has the performance of sufficiently maintaining the mechanical strength of the ion exchange membrane.

In addition, the variation of lamination described here is an example, and considering the desired layer structure, physical properties, etc. of a film body, a suitable lamination pattern (for example, the combination of each layer, etc.) can be selected, and then co-extruded.

Further, in order to further improve the electrical performance of the ion exchange membrane, a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor is further interposed between the first layer and the second layer. It is also possible to use a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor instead of the layer.

The method for forming the fourth layer may be a method of separately preparing a fluorine-containing polymer having a carboxylic acid group precursor and a fluorine-containing polymer having a sulfonic acid group precursor, and then mixing the monomers with the carboxylic acid group precursor and the sulfonic acid group precursor. The method of copolymerizing the monomer which has the thing may be used.

In the case where the fourth layer is configured as an ion exchange membrane, the coextruded film of the first layer and the fourth layer is molded, and the third layer and the second layer are filmed independently of this, by the method described above. You may laminate | stack and three layers of a 1st layer / 4th layer / 2nd layer may be film-formed by coextrusion at once.

In this case, the direction in which the extruded film flows is the MD direction. In this way, a membrane body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material.

In addition, the ion exchange membrane preferably has a protruding portion, that is, a convex portion, made of a fluorine-containing polymer having a sulfonic acid group, on the surface side of the sulfonic acid layer. It does not specifically limit as a method of forming such a convex part, The well-known method of forming a convex part in the resin surface can be employ | adopted. Specifically, the method of embossing on the surface of a film main body is mentioned, for example. For example, when the said composite film, reinforcing material, etc. are integrated, the said convex part can be formed by using the release paper previously embossed. When forming a convex part by embossing, control of the height and placement density of a convex part can be performed by controlling the emboss shape (shape of a release paper) to be transferred.

(5) hydrolysis process

In the step (5), the membrane body obtained in the step (4) is hydrolyzed to convert the ion exchanger precursor into the ion exchanger (hydrolysis step).

In the step (5), the elution hole can be formed in the membrane main body by dissolving and removing the sacrificial yarn contained in the membrane main body with an acid or an alkali. In addition, the sacrificial yarn may remain in the communication hole without being completely dissolved and removed. In addition, the sacrificial yarn remaining in the communication hole may be dissolved and removed by the electrolytic solution when the ion exchange membrane is provided for electrolysis.

The sacrificial yarn is soluble in acid or alkali in the ion exchange membrane production process or in an electrolytic environment, and communication holes are formed in the site by dissolving the sacrificial material.

The step (5) can be performed by immersing the membrane body obtained in the step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (dimethyl sulfoxide) can be used.

It is preferable that the said mixed solution contains 2.5-4.0 N of KOH, and contains 25-35 mass% of DMSO.

As temperature of hydrolysis, it is preferable that it is 70-100 degreeC. The higher the temperature, the thicker the apparent thickness. More preferably, it is 75-100 degreeC.

It is preferable that it is 10 to 120 minutes as time of hydrolysis. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes.

Here, the process of forming a communication hole by eluting a sacrificial yarn is demonstrated in detail. 122 (a) and 122 (b) are schematic diagrams for explaining a method of forming a communication hole of an ion exchange membrane.

In FIGS. 122A and 122B, only the communication holes 504 formed by the reinforcement yarn 52, the sacrificial yarn 504a, and the sacrificial yarn 504a are shown. The illustration is omitted.

First, the reinforcement yarn 52 which comprises a reinforcing core material in an ion exchange membrane, and the sacrificial yarn 504a for forming the communication hole 504 in an ion exchange membrane are used as a knitted reinforcement material. And the communication hole 504 is formed by eluting the sacrificial yarn 504a in the process (5).

According to the method described above, the knitting method of the reinforcing yarn 52 and the sacrificial yarn 504a may be adjusted in accordance with the arrangement of the reinforcing core and the communication hole in the membrane main body of the ion exchange membrane.

In (a) of FIG. 122, although the reinforcement of the plain weave which woven the reinforcement yarn 52 and the sacrificial yarn 504a in both the longitudinal direction and the horizontal direction in the ground is illustrated, the reinforcement yarn in a reinforcement material as needed. The arrangement of the 52 and the victim 504a can be changed.

(6) coating process

In the step (6), the coating layer can be formed by preparing a coating liquid containing the inorganic particles obtained by gemstone grinding or melting of the gemstone and a binder, and applying and drying the coating liquid on the surface of the ion exchange membrane obtained in the step (5). .

As a binder, after hydrolyzing the fluorine-containing polymer having an ion exchange group precursor with an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH), it is immersed in hydrochloric acid to replace the counter ion of the ion exchange group with H ⁺ . One binder (eg, a fluorine-containing polymer having a carboxyl or sulfo group) is preferred. Since it becomes easy to melt | dissolve in water and ethanol mentioned later by this, it is preferable.

This binder is dissolved in a solution in which water and ethanol are mixed. Moreover, the preferable volume ratio of water and ethanol is 10: 1-1:10, More preferably, it is 5: 1-1: 5, More preferably, it is 2: 1-1: 2. In the solution thus obtained, the inorganic particles are dispersed by a ball mill to obtain a coating solution. At this time, the average particle diameter of a particle | grains, etc. can also be adjusted by adjusting the time and the rotation speed at the time of dispersion. In addition, the preferable compounding quantity of an inorganic particle and a binder is as above-mentioned.

The concentration of the inorganic particles and the binder in the coating liquid is not particularly limited, but is preferably a light coating liquid. Thereby, it becomes possible to apply | coat uniformly to the surface of an ion exchange membrane.

In addition, when dispersing the inorganic particles, a surfactant may be added to the dispersion. As surfactant, a nonionic surfactant is preferable, For example, HS-210, NS-210, P-210, E-212 by Nichi-yu Corporation, etc. are mentioned.

An ion exchange membrane is obtained by apply | coating the obtained coating liquid to the surface of an ion exchange membrane by spray coating or roll coating.

[Microporous membrane]

As described above, the microporous membrane of the present embodiment is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various microporous membranes can be applied.

Although the porosity of the microporous membrane of this embodiment is not specifically limited, For example, it can be 20-90, Preferably it is 30-85. The porosity can be calculated by the following formula, for example.

Porosity = (1- (Dry Film Weight in Dry State) / (Volume calculated from the thickness, width and length of the film and weight calculated from the density of the film material)) × 100

Although the average pore diameter of the microporous membrane of this embodiment is not specifically limited, For example, it can be 0.01 micrometer-10 micrometers, Preferably it is 0.05 micrometer-5 micrometers. The average pore diameter is, for example, the film is vertically cut in the thickness direction, and the cut surface is observed by FE-SEM. It can obtain | require by measuring and averaging about 100 points of the diameter of the hole observed.

Although the thickness of the microporous film of this embodiment is not specifically limited, For example, it can be 10 micrometers-1000 micrometers, Preferably it is 50 micrometers-600 micrometers. The said thickness can be measured using a micrometer (made by Mitsutoyo Corporation) etc., for example.

Specific examples of the microporous membrane as described above include those described in Zirfon Perl UTP 500, International Publication No. 2013-183584, International Publication No. 2016-203701, etc. manufactured by Agfa.

In the manufacturing method of the electrolytic cell which concerns on this embodiment, it is a thing that a diaphragm contains the 1st ion exchange resin layer and the 2nd ion exchange resin layer which has an EW (ion exchange equivalent) different from this 1st ion exchange resin layer. desirable. Moreover, it is preferable that a diaphragm contains the 1st ion exchange resin layer and the 2nd ion exchange resin layer which has a functional group different from this 1st ion exchange resin layer. An ion exchange equivalent can be adjusted with the functional group to introduce | transduce, and the functional group which can be introduce | transduced is as above-mentioned.

(Hydraulic)

As the electrolytic cell in this embodiment, the electrolytic cell in the case of performing electrolysis has a structure which changed the ion exchange membrane in the electrolytic cell in the case of performing the above-mentioned salt electrolysis to a microporous membrane. In addition, since the raw material to be supplied is water, it differs from the electrolytic cell in the case of performing the above-mentioned salt electrolysis. As for other configurations, the same configuration as the electrolytic cell in the case of performing salt electrolysis can also be adopted. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. However, in the case of hydrolysis, since oxygen gas is only generated in the anode chamber, the same material as the cathode chamber is used. Can be used. For example, nickel etc. can be mentioned. In addition, the anode coating is suitably a catalyst coating for oxygen generation. Examples of catalyst coatings include metals, oxides, hydroxides, and the like of platinum group metals and transition metals. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used.

Example

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited at all by the following examples.

<Verification of the first embodiment>

As described below, an experimental example corresponding to the first embodiment (hereinafter simply referred to as "an example" in the section of <verification of the first embodiment>) and an experimental example not corresponding to the first embodiment (Simply referred to as "comparative example" in the following section in <Verification of the first embodiment>) was prepared, and these were evaluated by the following method. The detail is demonstrated, referring FIGS. 10-21 suitably.

〔Assessment Methods〕

(1) Opening rate

The electrode was cut out to a size of 130 mm x 100 mm. The average value which measured ten points of surface uniformly was computed using the dejimatic thickness gauge (Mitsutoyo Corporation make, minimum indication 0.001mm). The volume was computed using this as thickness of an electrode (gauge thickness). Then, the mass was measured by the electronic balance, and the porosity or the porosity was computed from the specific gravity of metal (specific gravity of nickel = 8.908 g / cm <3>, specific gravity of titanium = 4.506 g / cm <3>).

Porosity (porosity) (%) = (1- (electrode mass) / (electrode volume × specific gravity of metal)) × 100

(2) mass per unit area (mg / cm 2)

The electrode was cut out to a size of 130 mm x 100 mm, and the mass was measured by electronic balance. The mass per unit area was computed by dividing the value by area (130 mm x 100 mm).

(3) Force applied per unit mass and unit area (1) (adhesive force) (N / mg · cm 2)

[Method (i)]

A tensile compression tester was used for the measurement (Imada Co., Ltd., tester main body: SDT-52NA type tensile compression tester, weighting meter: SL-6001 type weighting machine).

The blast process was performed with the alumina of particle number 320 on the nickel plate of thickness 1.2mm and width-and-length 200mm. The arithmetic mean surface roughness Ra of the nickel plate after blasting was 0.7 micrometers. Here, the stylus type surface roughness measuring instrument SJ-310 (Mitsutoyo Co., Ltd.) was used for surface roughness measurement. The measurement sample was installed on the surface plate parallel to the ground, and the arithmetic mean roughness Ra was measured under the following measurement conditions. The measurement described the average value at the time of six implementations.

<Shape of the needle> Cone taper angle = 60 °, tip radius = 2 μm, static measuring force = 0.75 mN

<Roughness standard> JIS2001

<Evaluation curve> R

<Filter> GAUSS

<Cut-off value λc> 0.8 mm

<Cut off value λs> 2.5 μm

<Number of Sections> 5

<Jeonju, Huju> Yes

The nickel plate was fixed to the lower chuck of the tensile compression tester so as to be vertical.

As the diaphragm, the following ion exchange membrane A was used.

As a reinforcing core material, it was made of polytetrafluoroethylene (PTFE) and 90 denier monofilament was used (hereinafter referred to as PTFE company). As the sacrificial yarn, a yarn in which twisted polyethylene denephthalate (PET) of 35 deniers and 6 filaments was applied 200 times / m was used (hereinafter referred to as PET yarn). First, in each of the two directions of TD and MD, the woven fabric was plain so that two lines of PTFE yarn were disposed between 24 lines / inch and two sacrificed yarns were adjacent to adjacent PTFE yarns. The obtained woven fabric was crimped with a roll to obtain a woven fabric having a thickness of 70 µm.

Next, Resin A, CF ₂ = CF ₂ , a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ , having an ion exchange capacity of 0.85 mg equivalent / g. And Resin B of a dry resin having a copolymer of CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and having an ion exchange capacity of 1.03 mg equivalent / g.

Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 µm and a resin B layer of 104 µm was obtained by a coextrusion T die method.

Subsequently, a hot plate having a heating source and a vacuum source therein and having fine holes on its surface was laminated in the order of release paper (conical embossing having a height of 50 μm), reinforcing material and film X, and hot plate. After heating and pressure-reducing for 2 minutes on the conditions of surface temperature 223 degreeC, and the pressure reduction degree 0.067 MPa, the composite film was obtained by removing a release paper.

The obtained composite membrane was saponified by immersing for 20 minutes in 80 degreeC aqueous solution containing 30 mass% of dimethyl sulfoxide (DMSO), and 15 mass% of potassium hydroxide (KOH). Then, it was immersed in 50 degreeC aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour, the counter ion of the ion exchange group was substituted by Na, and it washed with water continuously. Furthermore, it dried at 60 degreeC.

Further, a suspension obtained by adding 20 mass% of zirconium oxide having a primary particle size of 1 μm to a 5 mass% ethanol solution of the acid-type resin of the resin B was dispersed, sprayed onto both surfaces of the composite membrane by a suspension spray method, and A coating was formed on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconium oxide was 0.5 mg / cm 2 as measured by fluorescence X-ray measurement. In addition, the average particle diameter was measured by the particle size distribution meter ("SALD (trademark) 2200" by Shimadzu Corporation).

The ion exchange membrane (diaphragm) obtained above was immersed in pure water for 12 hours or more, and used for the test. The nickel plate was sufficiently wetted with pure water and brought into contact with water under tension. At this time, it installed so that the position of the upper surface of a nickel plate and an ion exchange membrane may match.

The electrolytic electrode sample (electrode) used for the measurement was cut | disconnected to 130 mm long. Ion exchange membrane A was cut out to 170 mm in length and width. One side of the electrode was sandwiched between two stainless plates (1 mm in thickness, 9 mm in length, and 170 mm in width), and the stainless plate and the center of the electrode were aligned so as to be aligned, and then fixed evenly with four clips. The center of the stainless plate was fitted to the chuck above the tensile compression tester, and the electrodes were suspended. At this time, the load applied to the tester was 0N. First, the stainless plate, the electrode, and the clip assembly were removed from the tensile compression tester, and soaked in a batt containing pure water in order to sufficiently wet the electrode with pure water. After that, the center of the stainless steel plate was placed on the upper chuck of the tensile compression tester and the electrode was suspended.

The upper chuck of the tensile compression tester was lowered, and the electrolytic electrode sample was adhered to the surface of the ion exchange membrane by pure surface tension. The adhesive surface at this time was 130 mm in width and 110 mm in length. The pure water put in the bottle was sprayed on the electrode and the whole ion exchange membrane, and the diaphragm and the electrode were made wet again. Then, the roller which wound the EPDM sponge rubber of the independent foaming type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) was pressed lightly from the top of the electrode, and it rolled downwards from the top to remove the extra pure water. The roller was rolled only once.

Weight measurement was started by raising the electrode at a rate of 10 mm / min, and the weight when the overlapping portion of the electrode and the diaphragm became 130 mm in width and 100 mm in length was recorded. This measurement was performed three times and the average value was calculated.

This average value was divided by the area of the overlapped portion of the electrode and the ion exchange membrane and the electrode mass of the portion overlapped with the ion exchange membrane to calculate the force (1) applied per unit mass and unit area. The electrode mass of the part which overlapped with the ion exchange membrane was calculated | required by the proportional calculation from the value obtained from the mass per unit area (mg / cm <2>) of said (2).

The environment of the measurement room was 23 ± 2 ° C. and 30 ± 5% relative humidity.

In addition, when the electrode used by the Example and the comparative example was adhere | attached on the ion exchange membrane bonded by the surface tension to the nickel plate fixed vertically, it was self-supporting and adhered, without flowing down or peeling.

10, the schematic diagram of the evaluation method of the applied force 1 was shown.

In addition, the minimum of the measurement of the tensile tester was 0.01 (N).

(4) Force applied per unit mass and unit area (2) (adhesive force) (N / mg · cm 2)

[Method (ii)]

A tensile compression tester was used for the measurement (Imada Co., Ltd., tester main body: SDT-52NA type tensile compression tester, weighting meter: SL-6001 type weighting machine).

The same nickel plate as the method (i) was fixed to the lower chuck of the tensile compression tester so as to be vertical.

The electrolytic electrode sample (electrode) used for the measurement was cut | disconnected to 130 mm long. Ion exchange membrane A was cut out to 170 mm in length and width. One side of the electrode was sandwiched between two stainless plates (1 mm in thickness, 9 mm in length, and 170 mm in width), and the stainless plate and the center of the electrode were aligned so as to be aligned, and then fixed evenly with four clips. The center of the stainless plate was fitted to the chuck above the tensile compression tester, and the electrodes were suspended. At this time, the load applied to the tester was 0N. First, from the tensile compression tester, the stainless plate, the electrode, and the clip assembly were removed, and soaked in a batt containing pure water in order to sufficiently wet the electrode with pure water. Then, the center of the stainless plate was pinched again on the chuck | zipper of a tension compression tester, and the electrode was suspended.

The upper chuck of the tensile compression tester was lowered, and the electrolytic electrode sample was adhered to the nickel plate surface by the surface tension of the solution. The adhesive surface at this time was 130 mm in width and 110 mm in length. The pure water in the bottle was sprayed on the electrode and the whole of the nickel plate, and the nickel plate and the electrode were made sufficiently wet again. Then, the roller which wound the EPDM sponge rubber of the independent foaming type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) was pressed lightly from the top of the electrode, and was rolled from the top to the bottom, and the excess solution was removed. The roller was rolled only once.

Weight measurement was started by raising the electrode at a rate of 10 mm / min, and the weight when the overlapping portion in the longitudinal direction of the electrode and the nickel plate became 100 mm was recorded. This measurement was performed three times and the average value was calculated.

The average value was divided by the area of the overlapped portion of the electrode and the nickel plate and the electrode mass of the portion overlapped with the nickel plate to calculate the force 2 applied per unit mass and unit area. The electrode mass of the part which overlapped with the diaphragm was calculated | required by the proportional calculation from the value obtained from the mass per unit area (mg / cm <2>) of said (2).

In addition, the environment of the measurement chamber was 23 ± 2 ° C. and 30 ± 5% relative humidity.

In addition, when the electrode used by the Example and the comparative example was adhere | attached by the surface tension to the nickel plate fixed vertically, it adhered by self-supporting, without flowing down or peeling.

In addition, the minimum of the measurement of the tensile tester was 0.01 (N).

(5) 280 mm diameter cylindrical winding evaluation method (1) (%)

(Membrane and cylinder)

Evaluation method (1) was implemented in the following procedures.

The ion exchange membrane A (diaphragm) created in [Method (i)] was cut into a size of 170 mm in width and length. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. In Comparative Examples 10 and 11, since the electrode was integrated with the ion exchange membrane by heat press, an integral body of the ion exchange membrane and the electrode was prepared (the electrode was 130 mm long). After the ion exchange membrane was sufficiently immersed in pure water, it was placed on the curved surface of a pipe made of plastic (polyethylene) having an outer diameter of 280 mm. Then, the excess solution was removed with the roller which wound the EPDM sponge rubber of the independent foaming type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm). The roller rolled on the ion exchange membrane toward the left side to the right side of the schematic diagram shown in FIG. The roller was rolled only once. After 1 minute, the ratio of the part where the ion exchange membrane and the pipe electrode made of plastic with an outer diameter of 280 mm were in close contact was measured.

(6) 280 mm diameter cylindrical winding evaluation method (2) (%)

(Membrane and electrode)

Evaluation method (2) was implemented in the following procedures.

The ion exchange membrane A (diaphragm) created in [Method (i)] was cut to a size of 170 mm in width and length, and the electrode was cut to 130 mm in width and length. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminated body was placed on the curved surface of the plastic (polyethylene) pipe of outer diameter 280 mm so that an electrode might become outer side. Subsequently, while pressing the roller which wound EPDM sponge rubber of independent foam type of thickness 5mm in a vinyl chloride pipe (outer diameter 38mm) lightly from the top of an electrode, it rolls toward the right side from the left side of the schematic diagram shown in FIG. Removed. The roller was rolled only once. After 1 minute, the ratio of the part where the ion exchange membrane and the electrode were in close contact was measured.

(7) 145 mm diameter cylindrical winding evaluation method (3) (%)

(Membrane and electrode)

The evaluation method (3) was implemented in the following procedures.

The ion exchange membrane A (diaphragm) created in [Method (i)] was cut to a size of 170 mm in width and length, and the electrode was cut to 130 mm in width and length. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. The laminate was placed on the curved surface of a pipe made of plastic (polyethylene) having an outer diameter of 145 mm so that the electrode was outside. Subsequently, while pressing the roller which wound EPDM sponge rubber of the independent foam type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) lightly from the top of an electrode, it rolls toward the right side from the left side of the schematic diagram shown in FIG. Removed. The roller was rolled only once. After 1 minute, the ratio of the part where the ion exchange membrane and the electrode were in close contact was measured.

(8) handling (response evaluation)

(A) The ion-exchange membrane A (diaphragm) created by [method (i)] was cut into the size of 170 mm horizontally and 95 x 110 mm. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. In each Example, the ion exchange membrane and the electrode were fully immersed in three kinds of solutions of sodium bicarbonate aqueous solution, 0.1N NaOH aqueous solution, and pure water, and were laminated and set on a Teflon plate. The distance between the positive electrode cell and the negative electrode cell used in the electrolytic evaluation was set to about 3 cm, and the finely set laminated body was lifted, and the operation which inserted and pinched in between was performed. When this operation was performed, it was checked while operating whether the electrode was not twisted or dropped.

(B) The ion exchange membrane A (diaphragm) created in [Method (i)] was cut to a size of 170 mm in width and length, and the electrode was cut to 95 × 110 mm. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. In each Example, the ion exchange membrane and the electrode were fully immersed in three kinds of solutions of sodium bicarbonate aqueous solution, 0.1N NaOH aqueous solution, and pure water, and were laminated and set on a Teflon plate. The two adjacent corners of the membrane part of the laminated body were grasped by hand, and the laminated body was lifted up so that it was vertical. From this state, it moved so that the two edge | edges grasped | handed by hand might be made to become convex and concave. This was repeated once more to confirm the followability of the electrode to the film. The result was evaluated in four steps of 1-4 based on the following indicators.

1: Good handling

2: Handleable

3: difficult handling

4: almost impossible to handle

Here, about the sample of the comparative example 5, handling was carried out in the same size as the large electrolytic cell of the size of 1.3 m x 2.5 m and the ion exchange membrane in the size of 1.5 m x 2.8 m. The evaluation result ("3") of the comparative example 5 was made into the index which evaluates the difference at the time of making evaluation of said (A), (B), and large size. That is, when the result of evaluating a small laminated body is "1" and "2", even if it was set as the large size, it evaluated that there was no problem in handling property.

(9) Electrolytic evaluation (voltage (V), current efficiency (%), salt concentration in caustic soda (ppm, 50% equivalent))

The electrolytic performance was evaluated by the following electrolytic experiment.

A positive electrode cell (anode terminal cell) made of titanium having a positive electrode chamber provided with a positive electrode and a negative electrode cell having a negative electrode chamber (cathode terminal cell) made of nickel provided with a negative electrode were opposed to each other. A pair of gaskets were arrange | positioned between cells, and the laminated body (the laminated body of an ion exchange membrane A and an electrode for electrolysis) was sandwiched between a pair of gaskets. Then, an anode cell, a gasket, a laminate, a gasket, and a cathode were brought into close contact to obtain an electrolysis cell, and an electrolytic cell containing the same was prepared.

As an anode, it produced by apply | coating, drying, and baking the mixed solution of ruthenium chloride, iridium chloride, and titanium tetrachloride on the titanium base material which carried out the blast and acid etching process as a pretreatment. The anode was fixed to the anode chamber by welding. As the negative electrode, those described in Examples and Comparative Examples were used. Nickel expanded metal was used as an electrical power collector of a negative electrode chamber. The size of the current collector was 95 mm in length × 110 mm in width. As the metal elastic body, a mattress woven from nickel thin wire was used. The mattress, which is a metal elastomer, was placed on the current collector. A nickel wire having a diameter of 150 µm was covered with a flat nickel mesh having a size of 40 mesh, and four corners of the Ni mesh were fixed to a current collector with a string made of Teflon (registered trademark). This Ni mesh was used as a feeder. In this electrolytic cell, the repulsive force of the mattress which is a metal elastic body is used, and it has a zero gap structure. As the gasket, a rubber gasket made of EPDM (ethylene propylene diene) was used. As a diaphragm, the ion exchange membrane A (160 mm long) created by [method (i)] was used.

Salt electrolysis was performed using the said electrolysis cell. The brine concentration (sodium chloride concentration) of the anode chamber was adjusted to 205 g / L. The sodium hydroxide concentration of the cathode chamber was adjusted to 32 mass%. Each temperature of the anode chamber and the cathode chamber was adjusted such that the temperature in each electrolytic cell was 90 ° C. Salt electrolysis was performed at a current density of 6 kA / m 2, and the salt concentration in voltage, current efficiency, and caustic soda was measured. Here, the current efficiency is a ratio of the amount of generated caustic soda to the current that flows, and the current efficiency decreases when impurity ions or hydroxide ions, not sodium ions, move the ion exchange membrane by the current that flows. The current efficiency was obtained by dividing the number of moles of caustic soda generated at a given time by the number of moles of electrons of the current flowing therein. The number of moles of caustic soda was determined by recovering the caustic soda produced by electrolysis into a poly tank and measuring the mass thereof. The sodium chloride concentration in caustic soda represented the value converted from caustic soda to 50%.

Table 1 also shows the specifications of the electrodes and feeders used in Examples and Comparative Examples.

(11) Measurement of the thickness of the catalyst layer, the electrode base for electrolysis, the thickness of the electrode

The thickness of the electrode base material for electrolysis computed the average value which measured 10 points uniformly in-plane using the dejimatic thickness gauge (Mitsutoyo Corporation make, minimum display 0.001mm). This was made into the thickness (gauge thickness) of the electrode base material for electrolysis. The thickness of the electrode computed the average value which measured 10 points uniformly in-plane with the dejimatic thickness gauge similarly to the electrode base material. This was made into the thickness (gauge thickness) of an electrode. The thickness of the catalyst layer was obtained by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

(12) elastic deformation test of electrode

The ion-exchange membrane A (diaphragm) and the electrode which were created by [method (i)] were cut | judged to the size of 110 mm width and height. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. After the laminate was fabricated by overlapping the ion exchange membrane and the electrode under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, as shown in FIG. Wound up. The wound laminate was fixed using a binding band made of polyethylene so as not to be peeled or relaxed from the PVC pipe. It kept in this state for 6 hours. Then, the binding band was removed and the laminated body was loosened from the pipe made from PVC. Only the electrode was placed on the surface plate, and the heights L ₁ and L ₂ of the portion floating from the surface plate were measured to obtain an average value. This value was used as an index of electrode deformation. That is, the smaller the value is, the harder it is to deform.

In addition, when using an expanded metal, when winding up, there are two types, SW direction and LW direction. In this test, it wound up to SW direction.

Moreover, about the softness after plastic deformation was evaluated about the electrode which the deformation | transformation (electrode which did not return to the original flat state) by the method as shown in FIG. That is, the electrode which had a deformation | transformation was placed on the diaphragm fully immersed in pure water, the one end was fixed, the opposing edge part which floated was pressed to the diaphragm, the force was opened, and it evaluated whether the electrode which a deformation | transformation followed the diaphragm.

(13) membrane damage evaluation

As the diaphragm, the following ion exchange membrane B was used.

As the reinforcing core material, polytetrafluoroethylene (PTFE), which was made into a yarn shape by applying a twist of 900 times / m to a 100 denier tape yarn (hereinafter referred to as PTFE company). As a sacrificial warp yarn, a yarn in which 35 denier and 8 filament polyethylene terephthalate (PET) was twisted 200 times / m was used (hereinafter referred to as PET yarn). As a weft sacrificial yarn, a yarn in which 35 denier and 8 filament polyethylene terephthalate (PET) was twisted 200 times / m was used. First, a PTFE woven fabric was plain weave so that two lines of 24 lines / inch and a sacrificial yarn were disposed between adjacent PTFE yarns to obtain a woven fabric having a thickness of 100 µm.

Next, CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ is a copolymer of dry resin with an ion exchange capacity of 0.92 mg equivalent / g (CF), CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F is a copolymer of a dry resin (B1) having an ion exchange capacity of 1.10 mg equivalent / g. Using these polymers (A1) and (B1), the two-layer film X having the thickness of the polymer (A1) layer of 25 µm and the polymer (B1) layer of 89 µm was obtained by the coextrusion T die method. In addition, the ion exchange capacity of each polymer showed the ion exchange capacity when the ion exchanger precursor of each polymer was hydrolyzed and converted into the ion exchanger.

In addition, separately prepared polymer (B2) of a dry resin having a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and having an ion exchange capacity of 1.10 mg equivalent / g. This polymer was single-layer extruded and the film Y of 20 micrometers was obtained.

Subsequently, on a hot plate having a heating source and a vacuum source therein and having micropores on the surface thereof, they were laminated in the order of the release paper, the film Y, the reinforcing material and the film X, and the hot plate temperature was 225 ° C. and the pressure reduction degree was 0.022 MPa. After heating and pressure-reducing for 2 minutes on conditions, the composite film was obtained by removing a release paper. The obtained composite membrane was saponified by immersion in an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) for 1 hour, and then immersed in 0.5 N NaOH for 1 hour to replace ions attached to the ion exchanger with Na. Continually washed. Furthermore, it dried at 60 degreeC.

In addition, hydrolyzed polymer (B3) of a dry resin having a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F, having an ion exchange capacity of 1.05 mg equivalent / g. After that, it was in acid form by hydrochloric acid. Zirconium oxide particles having an average particle diameter of 0.02 µm were prepared in a solution obtained by dissolving the polymer (B3 ') in the acid form in a 50/50 (mass ratio) mixture of water and ethanol at a ratio of 5% by mass. B3 ') and the mass ratio of zirconium oxide particle | grains were added so that it might be 20/80. Thereafter, the mixture was dispersed in a suspension of zirconium oxide particles in a ball mill to obtain a suspension.

This suspension was applied to both surfaces of the ion exchange membrane by the spray method and dried to obtain an ion exchange membrane B having a coating layer containing a polymer (B3 ') and zirconium oxide particles. It was 0.35 mg / cm <2> when the coating density of zirconium oxide was measured by the fluorescent X-ray measurement.

The positive electrode used the same thing as (9) electrolytic evaluation.

As the negative electrode, those described in Examples and Comparative Examples were used. The current collector, the mattress, and the electric power feeder of the negative electrode chamber used the same thing as (9) Electrolytic evaluation. In other words, the Ni mesh is used as the feeder, and the repulsive force of the mattress, which is a metal elastic body, is used to form a zero gap structure. The gasket also used the same thing as (9) electrolytic evaluation. An ion exchange membrane B prepared by the above method was used as the diaphragm. That is, the electrolytic cell similar to (9) was prepared except the sandwiching body of the ion exchange membrane B and the electrode for electrolysis was sandwiched between a pair of gaskets.

Salt electrolysis was performed using the said electrolysis cell. The brine concentration (sodium chloride concentration) of the anode chamber was adjusted to 205 g / L. The sodium hydroxide concentration of the cathode chamber was adjusted to 32 mass%. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell was 70 ° C. Salt electrolysis was performed at a current density of 8 kA / m 2. Electrolysis was stopped 12 hours after the start of the electrolysis, and the ion exchange membrane B was taken out and the damage state was observed.

"0" means no damage. "1-3" means that there is damage, and the larger the number, the greater the degree of damage.

(14) air resistance of the electrode

The air permeation resistance of the electrode was measured using the air permeability tester KES-F8 (trade name, Kato Tech Co., Ltd.). The unit of ventilation resistance value is kPa * s / m. The measurement was performed 5 times and the average value is shown in Table 2. The measurement was performed under the following two conditions. In addition, the temperature of the measurement chamber was 24 degreeC and the relative humidity was 32%.

ㆍ Measurement condition 1 (ventilation resistance 1)

Piston Speed: 0.2 cm / s

Aeration amount: 0.4 cc / ㎠ / s

Measuring range: SENSE L (low)

Sample size: 50 mm x 50 mm

ㆍ Measurement condition 2 (ventilation resistance 2)

Piston Speed: 2 cm / s

Aeration amount: 4 cc / ㎠ / s

Measuring range: SENSE M (medium) or H (high)

Sample size: 50 mm x 50 mm

Example 1

As an electrode base material for negative electrode electrolysis, the electrolytic nickel foil whose gauge thickness is 16 micrometers was prepared. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. Arithmetic mean roughness Ra of the roughened surface was 0.71 micrometer. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted.

A circular hole was drilled into this nickel foil by punching to obtain a porous foil. Opening rate was 49%.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of the electrode produced in Example 1 was 24 µm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side. In addition, it is the total thickness of ruthenium oxide and cerium oxide.

Table 2 shows the measurement results of the adhesive force of the electrode produced by the above method. Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2.

The electrode produced by the above method was cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode is made to face the position near the center of the carboxylic acid layer side of the ion exchange membrane A (size is 160 mm x 160 mm) produced by 0.1N NaOH aqueous solution equilibrated, It adhered by the surface tension of aqueous solution.

Even when the four corners of the membrane portion of the membrane-integrated electrode in which the membrane and the electrode were integrated were held, and the electrode was placed on the ground side and the membrane-integrated electrode was suspended to be parallel to the ground, the electrodes did not peel off or fall off. In addition, even when the both ends of one side were held and the membrane-integrated electrode was suspended so as to be perpendicular to the ground, the electrode did not peel off or fall off.

The membrane-integrated electrode was sandwiched between the anode cell and the cathode cell such that the surface on which the electrode was attached was the cathode chamber side. The cross-sectional structure forms a zero-gap structure from the cathode chamber side in the order of a current collector, a mattress, a nickel mesh feeder, an electrode, a film, and an anode.

Electrolytic evaluation was performed about the obtained electrode. The results are shown in Table 2.

It showed low voltage, high current efficiency and low caustic concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF (fluorescence X-ray analysis), the roughened surface remained almost 100% of the coating, and the non-roughened surface reduced the coating. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 2

Example 2 used electrolytic nickel foil whose gauge thickness is 22 micrometers as an electrode base material for negative electrode electrolysis. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. The arithmetic mean roughness Ra of the roughened surface was 0.96 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. The porosity was 44%. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 29 μm. The thickness of the catalyst layer was 7 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode. The coating was also formed on the unroughened side.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0033 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF, the roughened surface remained almost 100% of the coating, and the non-roughened surface reduced the coating. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 3

Example 3 used electrolytic nickel foil whose gauge thickness is 30 micrometers as an electrode base material for negative electrode electrolysis. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. The arithmetic mean roughness Ra of the roughened surface was 1.38 m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. The porosity was 44%. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 38 μm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF, roughly 100% coating remained in the roughened surface, and coating decreased in the non-roughened surface. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 4

Example 4 used electrolytic nickel foil whose gauge thickness is 16 micrometers as an electrode base material for negative electrode electrolysis. One surface of this nickel foil was roughened by electrolytic nickel plating. Arithmetic mean roughness Ra of the roughened surface was 0.71 micrometer. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. The porosity was 75%. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 24 μm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF, roughly 100% coating remained in the roughened surface, and coating decreased in the non-roughened surface. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 5

Example 5 prepared the electrolytic nickel foil whose gauge thickness is 20 micrometers as an electrode base material for negative electrode electrolysis. Both surfaces of this nickel foil were roughened by electrolytic nickel plating. The arithmetic mean roughness Ra of the roughened surface was 0.96 mu m. Both sides had the same roughness. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Opening rate was 49%. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 30 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after the electrolysis was measured by XRF, almost 100% of the coating remained on both sides. When compared with Examples 1-4, the opposite surface which does not oppose a film | membrane shows that favorable electrolytic performance can be exhibited even if there is little or no coating.

Example 6

Example 6 evaluated similarly to Example 1 except having performed coating to the electrode base material for negative electrode electrolysis by ion plating, and the result was shown in Table 2. In addition, ion plating formed into a film at the film-forming pressure of 7x10 <^-2> Pa in argon / oxygen atmosphere using the heating temperature of 200 degreeC and Ru metal target. The coating formed was ruthenium oxide.

The thickness of the electrode was 26 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 7

Example 7 created the electrode base material for negative electrode electrolysis by the electroforming method. The shape of the photomask was made into the shape which arranged the square of 0.485 mm x 0.485 mm lengthwise and horizontally at 0.15 mm space | interval. By performing exposure, image development, and electroplating in order, the nickel porous foil with a gauge thickness of 20 micrometers and a porosity of 56% was obtained. Arithmetic mean roughness Ra of the surface was 0.71 m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 37 μm. The thickness of the catalyst layer was 17 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 8

Example 8 was created by the electroforming method as an electrode base material for cathode electrolysis, and the gauge thickness was 50 micrometers and porosity 56%. Arithmetic mean roughness Ra of the surface was 0.73 m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 60 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 9

In Example 9, a nickel nonwoven fabric (manufactured by Nico Techno Co., Ltd.) having a gauge thickness of 150 µm and a porosity of 76% was used as the electrode substrate for cathode electrolysis. Nickel fiber diameter of the nonwoven fabric was about 40 micrometers, and basis weight was 300 g / m <2>. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 165 mu m. The thickness of the catalyst layer was 15 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 29 mm, and did not return to the original flat state. Therefore, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastic deformation was carried out, it was confirmed that the diaphragm could be contacted with a small force, and this electrode was found to have good handling property.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0612 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was good as "0".

Example 10

In Example 10, a nickel nonwoven fabric (manufactured by Nico Techno Co., Ltd.) having a gauge thickness of 200 µm and a porosity of 72% was used as the electrode substrate for cathode electrolysis. The nickel fiber diameter of the nonwoven fabric was about 40 micrometers, and basis weight was 500 g / m <2>. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 215 탆. The thickness of the catalyst layer was 15 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

Bar subjected to transformation test of the electrodes, the average value of L _1, L ₂ is 40 mm, it did not go back up to the original flat state. Therefore, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastic deformation was carried out, it was confirmed that the diaphragm could be contacted with a small force, and this electrode was found to have good handling property.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0164 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was good as "0".

Example 11

In Example 11, foamed nickel (manufactured by Mitsubishi Material Co., Ltd.) having a gauge thickness of 200 µm and a porosity of 72% was used as the electrode substrate for cathode electrolysis. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

In addition, the thickness of the electrode was 210 micrometers. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 17 mm and it did not return to the original flat state. Therefore, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastic deformation was carried out, it was confirmed that the diaphragm could be contacted with a small force, and this electrode was found to have good handling property.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0402 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was good as "0".

Example 12

In Example 12, a nickel mesh having a wire diameter of 50 µm, 200 mesh, a gauge thickness of 100 µm, and a porosity of 37% was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. Even if blasting was performed, the porosity did not change. Since it is difficult to measure the roughness of the wire mesh surface, in Example 12, at the time of blasting, the nickel plate of thickness 1mm was blast-processed simultaneously, and the surface roughness of the nickel plate was made into the surface roughness of the wire mesh. The arithmetic mean roughness Ra of one wire mesh was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 110 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0.5 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0154 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 13

In Example 13, a nickel mesh having a wire diameter of 65 µm, 150 mesh, a gauge thickness of 130 µm, and a porosity of 38% was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. Even if blasting was performed, the porosity did not change. Since it is difficult to measure the roughness of the wire mesh surface, in Example 13, the nickel plate of thickness 1mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was made into the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.66 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, the said evaluation was performed similarly to Example 1, and the result was shown in Table 2.

The thickness of the electrode was 133 mu m. The thickness of the catalyst layer was 3 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 6.5 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0124 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was also good at "0".

Example 14

In Example 14, the same substrate (gauge thickness 30 µm, porosity 44%) as in Example 3 was used as the electrode substrate for cathode electrolysis. The electrolytic evaluation was performed with the structure similar to Example 1 except having not provided the nickel mesh electric power feeder. That is, the cross-sectional structure of the cell forms a zero-gap structure from the cathode chamber side in the order of the current collector, the mattress, the film integrated electrode, and the anode, and the mattress functions as a power feeder. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 15

In Example 15, the same substrate (gauge thickness 30 µm, porosity 44%) as in Example 3 was used as the electrode substrate for cathode electrolysis. In place of the nickel mesh feeder, a negative electrode having a deteriorated and high electrolytic voltage used in Reference Example 1 was provided. Other than that, electrolytic evaluation was performed by the same structure as Example 1. That is, the cross-sectional structure of the cell is arranged in the order of the current collector, the mattress, and the negative electrode (functioning as a power feeder), the electrode for electrolysis (cathode), the diaphragm, and the positive electrode deteriorated from the cathode chamber side in order of zero gap structure. And the cathode whose deterioration has increased the electrolytic voltage functions as a feeder. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 16

As an electrode base material for positive electrode electrolysis, titanium foil whose gauge thickness is 20 micrometers was prepared. The roughening process was given to both surfaces of the titanium foil. The titanium foil was punched out, and a circular hole was drilled into a porous foil. The diameter of the hole was 1 mm and the porosity was 14%. Arithmetic mean roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. Ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L, iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) with a iridium concentration of 100 g / L, titanium tetrachloride (Wakkoyaku Industry Co., Ltd.), ruthenium element and iridium It mixed so that the molar ratio of an element and a titanium element might be 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred to prepare a positive electrode coating solution.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). After apply | coating the said coating liquid to titanium porous foil, it dried for 10 minutes at 60 degreeC, and baked for 10 minutes at 475 degreeC. After repeating these series of application | coating, drying, plasticity, and baking a series of operations, it baked at 520 degreeC for 1 hour.

The electrode produced by the above method was cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The ion exchange membrane A (size: 160 mm x 160 mm) prepared in [Method (i)] equilibrated with 0.1 N NaOH aqueous solution was brought into close contact with the surface tension of the aqueous solution at a position near the center of the sulfonic acid layer side.

The negative electrode was prepared in the following order. First, a nickel wire mesh of 150 µm in diameter and 40 mesh was prepared as a substrate. After performing blasting with alumina as pretreatment, it was immersed in 6N hydrochloric acid for 5 minutes, and it fully wash | cleaned and dried with pure water.

Next, a ruthenium chloride solution (Tanaka Precious Metal Industry Co., Ltd.) and cerium chloride (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Then, drying for 10 minutes at 50 degreeC, plasticity for 3 minutes at 300 degreeC, and baking for 10 minutes at 550 degreeC was performed. Then, baking was performed at 550 degreeC for 1 hour. A series of operations of these coating, drying, plasticity, and baking were repeated.

Nickel expanded metal was used as an electrical power collector of a negative electrode chamber. The size of the current collector was 95 mm in length × 110 mm in width. As the metal elastic body, a mattress woven from nickel thin wire was used. The mattress, which is a metal elastomer, was placed on the current collector. The negative electrode created by the above method was covered thereon, and four corners of the mesh were fixed to the current collector with a string made of Teflon (registered trademark).

Even if the four edges of the membrane portion of the membrane-integrated electrode in which the membrane and the anode were integrated were held, and the electrode was brought to the ground side and the membrane-integrated electrode was suspended so as to be parallel to the ground, the electrodes did not peel off or twisted. In addition, even when the both ends of one side were held and the membrane-integrated electrode was suspended so as to be perpendicular to the ground, the electrode did not peel off or fall off.

The positive electrode, which had been used in Reference Example 3, had a deteriorated and high electrolytic voltage fixed by welding, and the membrane-integrated electrode was sandwiched between the positive electrode cell and the negative electrode so that the surface on which the electrode was attached was on the positive electrode side. That is, the cross-sectional structure of the cell was arranged from the cathode chamber side in the order of the current collector, the mattress, the cathode, the diaphragm, the electrolytic electrode (titanium porous foil anode), and the anode deteriorated to increase the electrolytic voltage to form a zero gap structure. The positive electrode which deteriorated and the electrolytic voltage became high functioned as a power feeder. In addition, between the titanium porous foil anode and the anode which deteriorated and the electrolytic voltage became high, it was only physically contacting and was not fixed by welding.

Evaluation was performed similarly to Example 1 with this structure, and the result was shown in Table 2.

The thickness of the electrode was 26 μm. The thickness of the catalyst layer was 6 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 4 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0060 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 17

In Example 17, titanium foil having a gauge thickness of 20 µm and a porosity of 30% was used as the electrode substrate for positive electrode electrolysis. Arithmetic mean roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that evaluated in the same manner as in Example 16, and the results are shown in Table 2.

The thickness of the electrode was 30 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 5 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0030 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 18

In Example 18, titanium foil having a gauge thickness of 20 μm and a porosity of 42% was used as the electrode substrate for positive electrode electrolysis. Arithmetic mean roughness Ra of the surface was 0.38 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that evaluated in the same manner as in Example 16, and the results are shown in Table 2.

The thickness of the electrode was 32 mu m. The thickness of the catalyst layer was 12 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 2.5 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0022 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 19

In Example 19, titanium foil having a gauge thickness of 50 µm and a porosity of 47% was used as the electrode substrate for positive electrode electrolysis. Arithmetic mean roughness Ra of the surface was 0.40 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 16, and showed the result in Table 2.

The thickness of the electrode was 69 μm. The thickness of the catalyst layer was 19 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation test of the electrode was conducted, the average value of L ₁ and L ₂ was 8 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0024 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 20

In Example 20, a titanium nonwoven fabric having a gauge thickness of 100 µm, a titanium fiber diameter of about 20 µm, a basis weight of 100 g / m 2, and a porosity of 78% was used as the electrode substrate for anode electrolysis. Other than that evaluated in the same manner as in Example 16, and the results are shown in Table 2.

The thickness of the electrode was 114 탆. The thickness of the catalyst layer was 14 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 2 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0228 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 21

In Example 21, a titanium wire mesh having a gauge thickness of 120 μm, a titanium fiber diameter of about 60 μm, and 150 mesh was used as the electrode substrate for positive electrode electrolysis. The porosity was 42%. The blasting was performed with the alumina of particle number 320. Since it is difficult to measure the roughness of the wire mesh surface, in Example 21, the titanium plate of thickness 1mm was blasted simultaneously at the time of blasting, and the surface roughness of the titanium plate was made into the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.60 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that evaluated in the same manner as in Example 16, and the results are shown in Table 2.

The thickness of the electrode was 140 μm. The thickness of the catalyst layer was 20 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 10 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0132 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 22

In Example 22, a positive electrode deteriorated and a high electrolytic voltage was used in the same manner as in Example 16, and the same titanium nonwoven fabric as in Example 20 was used as the positive electrode feeder. In the same manner as in Example 15, a cathode deteriorated to increase the electrolytic voltage was used as the cathode feeder, and the same nickel foil electrode as in Example 3 was used as the cathode. The cross-sectional structure of the cell is arranged in the order of the current collector, the mattress, the deteriorated high voltage cathode, the nickel porous foil cathode, the diaphragm, the titanium nonwoven anode, and the deteriorated positive electrode voltage from the cathode chamber side to form a zero gap structure. The negative electrode and the positive electrode which are deteriorated and the electrolytic voltage increased are functioning as a power feeder. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode (anode) was 114 μm, and the thickness of the catalyst layer was 14 μm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode (anode). The thickness of the electrode (cathode) was 38 μm, and the thickness of the catalyst layer was 8 μm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode (cathode).

Sufficient adhesion was observed for both the positive and negative electrodes.

When the deformation test of the electrode (anode) was performed, the average value of L ₁ and L ₂ was 2 mm. When the deformation test of the electrode (cathode) was conducted, the average value of L ₁ and L ₂ was 0 mm.

The ventilation resistance of the electrode (anode) was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0228 (kPa · s / m) under measurement condition 2. The ventilation resistance of the electrode (cathode) was measured to be 0.07 (kPa · s / m) or less in Measurement 1 and 0.0027 (kPa · s / m) in Measurement Condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". Film damage evaluation of both the positive electrode and the negative electrode was also good as "0". In addition, in Example 22, the film damage evaluation was performed by attaching a cathode to one side of the diaphragm and attaching an anode to the other side of the diaphragm.

Example 23

In Example 23, a microporous membrane "Zirfon Perl UTP 500" manufactured by Agfa Corporation was used.

Zirfon membrane was used for the test after immersion in pure water for more than 12 hours. Otherwise, the above evaluation was performed in the same manner as in Example 3, and the results are shown in Table 2.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

As in the case where the ion exchange membrane was used as the diaphragm, sufficient adhesive force was observed, the microporous membrane and the electrode were in close contact with each other by the surface tension, and the handling property was "1".

Example 24

As an electrode base material for negative electrode electrolysis, carbon cloth woven of carbon fibers having a gauge thickness of 566 µm was prepared. The coating liquid for forming an electrode catalyst in this carbon cloth was prepared in the following procedure. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. An application roll wound with rubber (Inoac Corporation, E-4088 (trade name), thickness 10 mm) made of foamed EPDM (ethylene propylene diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride); It was installed so that the coating liquid always contacted. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of the produced electrode was 570 micrometers. The thickness of the catalyst layer was 4 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode. The thickness of the catalyst layer was the total thickness of ruthenium oxide and cerium oxide.

Electrolytic evaluation was performed about the obtained electrode. The results are shown in Table 2.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm.

The ventilation resistance of the electrode was measured, and found to be 0.19 (kPa · s / m) under measurement condition 1 and 0.176 (kPa · s / m) under measurement condition 2.

In addition, handling property was "2", and it was judged that it was handleable as a large laminated body.

The voltage was high, the film damage evaluation was "1", and the film damage was confirmed. This was considered to be because the NaOH generated at the electrode stayed at the interface between the electrode and the diaphragm and became high because the air permeation resistance of the electrode of Example 24 was large.

Reference Example 1

In Reference Example 1, a cathode used in a large electrolytic cell for eight years as a cathode and deteriorated to increase the electrolytic voltage was used. The negative electrode was placed on the mattress of the negative electrode chamber in place of the nickel mesh feeder, and the electrolytic evaluation was performed by sandwiching the ion exchange membrane A prepared in [Method (i)]. In Reference Example 1, the membrane-integrated electrode was not used, and the cross-sectional structure of the cell was formed from the cathode chamber side by arranging a current collector, a mattress, and a cathode, an ion exchange membrane A, and an anode deteriorated to increase the electrolytic voltage to form a zero gap structure. I was.

As a result of the electrolytic evaluation by this structure, the voltage was 3.04V, the current efficiency was 97.0%, and the salt concentration (50% conversion value) in caustic soda was 20 ppm. Since the cathode deteriorated, the result was a high voltage.

Reference Example 2

In Reference Example 2, a nickel mesh feeder was used as the cathode. That is, electrolysis was performed by the nickel mesh which was not catalyst coated.

A nickel mesh negative electrode was provided on the mattress of the negative electrode chamber, and the electrolytic evaluation was performed through the ion exchange membrane A created in [method (i)]. The cross-sectional structure of the electric cell of Reference Example 2 was arranged in the order of the current collector, the mattress, the nickel mesh, the ion exchange membrane A, and the anode from the cathode chamber side to form a zero gap structure.

As a result of electrolytic evaluation by this structure, the voltage was 3.38V, the current efficiency was 97.7%, and the salt concentration (50% conversion value) in caustic soda was 24 ppm. Since the negative catalyst was not coated, the result was a high voltage.

Reference Example 3

In Reference Example 3, a positive electrode used in a large electrolytic cell for about 8 years as a positive electrode and having a deteriorated electrolytic voltage was used.

The cross-sectional structure of the electrolytic cell of Reference Example 3 is arranged from the cathode chamber side in the order of the current collector, the mattress, the cathode, and the ion exchange membrane A prepared in [Method (i)], and the anode deteriorated to increase the electrolytic voltage. Formed.

As a result of the electrolytic evaluation by this structure, the voltage was 3.18V, the current efficiency was 97.0%, and the salt concentration (50% conversion value) in caustic soda was 22 ppm. Since the anode deteriorated, the result was a high voltage.

Comparative Example 1

In Comparative Example 1, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 33% after pull roll processing was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Comparative Example 1, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.68 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 114 탆. The thickness of the catalyst layer was 14 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 67.5 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.05 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) was 64%, and the result of the 145 mm cylindrical coil winding evaluation (3) was 22%, and the part from which an electrode and a diaphragm peeled was increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 13 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2.

Comparative Example 2

In Comparative Example 2, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 16% after pull roll processing was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Comparative Example 2, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 107 탆. The thickness of the catalyst layer was 7 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

The mass per unit area was 78.1 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.04 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) was 37%, and the result of the 145 mm cylindrical coil winding evaluation (3) was 25%, and the part from which an electrode and a diaphragm peeled off increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 18.5 mm. When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0176 (kPa · s / m) under measurement condition 2.

Comparative Example 3

In Comparative Example 3, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 40% after pull roll processing was used as an electrode base material for cathode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Comparative Example 3, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was defined as the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.70 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Coating on the electrode base for electrolysis was carried out by the same ion plating as in Example 6. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 110 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The force 1 applied per unit mass and unit area was a small value of 0.07 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is 80%, and the result of the 145 mm cylindrical coil winding evaluation (3) is 32%, and the part from which an electrode and a diaphragm peeled off increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 11 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0030 (kPa · s / m) under measurement condition 2.

[Comparative Example 4]

In Comparative Example 4, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 58% after pull roll processing was used as an electrode base material for cathode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Comparative Example 4, a nickel plate having a thickness of 1 mm was simultaneously blasted at the time of blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 109 탆. The thickness of the catalyst layer was 9 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

The force 1 applied per unit mass and unit area was a small value of 0.06 (N / mg · cm 2). For this reason, the result of the cylindrical winding evaluation 2 of 280 mm diameter was 69%, and the result of the cylindrical winding evaluation 3 of 145 mm diameter was 39%, and the part from which an electrode and a diaphragm peeled off increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 11.5 mm.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2.

[Comparative Example 5]

In Comparative Example 5, a nickel wire mesh having a gauge thickness of 300 µm and a porosity of 56% was used as the electrode substrate for cathode electrolysis. Since it is difficult to measure the surface roughness of the wire mesh, in Comparative Example 5, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Arithmetic mean roughness Ra was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 1, and showed the result in Table 2.

The thickness of the electrode was 308 mu m. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 49.2 (mg / cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation 2 was 88%, and the result of the 145 mm cylindrical coil winding evaluation 3 was 42%, and the part from which an electrode and a diaphragm peeled off increased. This is easy when the electrode is peeled off when handling the film-integrated electrode, and the electrode peels off from the film and falls during handling. There is a problem in handling property as "3". It actually operated in large size and evaluated as "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 23 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2.

Comparative Example 6

In Comparative Example 6, a nickel wire mesh having a gauge thickness of 200 μm and a porosity of 37% was used as the electrode substrate for negative electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the wire mesh, in Comparative Example 6, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.65 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, adhesiveness was performed similarly to Example 1 as a result of electrode electrolysis evaluation and the measurement of adhesive force. The results are shown in Table 2.

The thickness of the electrode was 210 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 56.4 mg / cm 2. For this reason, the adhesiveness of an electrode and a diaphragm was bad in 63% of the result of the 145 mm diameter coil winding evaluation method (3). This is easy when the electrode is peeled off when handling the film-integrated electrode, and the electrode peels off from the film and falls during handling. There is a problem in handling property as "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 19 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0096 (kPa · s / m) under measurement condition 2.

Comparative Example 7

In Comparative Example 7, a titanium expanded metal having a gauge thickness of 500 μm and a porosity of 17% after pull roll processing was used as the electrode substrate for positive electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Comparative Example 7, a titanium plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the titanium plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.60 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that evaluated in the same manner as in Example 16, and the results are shown in Table 2.

In addition, the thickness of the electrode was 508 micrometers. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 152.5 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.01 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is less than 5%, and the result of the 145 mm cylindrical coil winding evaluation (3) is less than 5%, and the part from which an electrode and a diaphragm peeled off increased. When handling the membrane-integrated electrode, the electrode was likely to be peeled off, and during the handling, the electrode was peeled off from the film and fell. Handling property also had a problem with "4". Membrane damage evaluation was "0".

Bar subjected to transformation test of the electrode, the electrode is not to be recalled while dried in the form of a PVC pipe, it could not measure the value of L _1, L _2.

The ventilation resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0072 (kPa · s / m) under measurement condition 2.

Comparative Example 8

In Comparative Example 8, a titanium expanded metal having a gauge thickness of 800 μm and a porosity of 8% after pull roll processing was used as the electrode substrate for positive electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Comparative Example 8, a titanium plate having a thickness of 1 mm was blasted at the same time in blasting, and the surface roughness of the titanium plate was defined as the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.61 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Otherwise, the above evaluation was performed in the same manner as in Example 16, and the results are shown in Table 2.

The thickness of the electrode was 808 μm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 251.3 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.01 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is less than 5%, and the result of the 145 mm cylindrical coil winding evaluation (3) is less than 5%, and the part from which an electrode and a diaphragm peeled off increased. When handling the membrane-integrated electrode, the electrode was likely to be peeled off, and during the handling, the electrode was peeled off from the film and fell. Handling property also had a problem with "4". Membrane damage evaluation was "0".

Bar subjected to transformation test of the electrode, the electrode is not to be recalled while dried in the form of a PVC pipe, it could not measure the value of L _1, L _2.

The ventilation resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0172 (kPa · s / m) under measurement condition 2.

Comparative Example 9

In Comparative Example 9, a titanium expanded metal having a gauge thickness of 1000 μm and a porosity of 46% after pull roll processing was used as the electrode substrate for positive electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Comparative Example 9, a titanium plate having a thickness of 1 mm was blasted at the same time in blasting, and the surface roughness of the titanium plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.59 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Otherwise, the above evaluation was performed in the same manner as in Example 16, and the results are shown in Table 2.

In addition, the thickness of the electrode was 1011 micrometers. The thickness of the catalyst layer was 11 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 245.5 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.01 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is less than 5%, and the result of the 145 mm cylindrical coil winding evaluation (3) is less than 5%, and the part from which an electrode and a diaphragm peeled off increased. When handling the membrane-integrated electrode, the electrode was likely to be peeled off, and during the handling, the electrode was peeled off from the film and fell. Handling property also had a problem with "4". Membrane damage evaluation was "0".

Bar subjected to transformation test of the electrode, the electrode is not to be recalled while dried in the form of a PVC pipe, it could not measure the value of L _1, L _2.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

Comparative Example 10

In Comparative Example 10, a membrane electrode assembly in which electrodes were thermocompression-bonded to a diaphragm was produced by referring to the prior document (Example of Japanese Patent Laid-Open No. 58-48686).

Electrode coating was carried out in the same manner as in Example 1, using a nickel expanded metal having a gauge thickness of 100 µm and a porosity of 33% as the electrode base material for cathode electrolysis. Thereafter, one surface of the electrode was subjected to deactivation in the following order. A polyimide adhesive tape (Chuko Chemical Co., Ltd.) was adhered to one side of the electrode, and a PTFE dispersion (Mitsui DuPont Florochemical Co., Ltd., 31-JR (trade name)) was applied to the opposite side and dried for 10 minutes in a muffle furnace at 120 ° C. I was. The polyimide tape was peeled off and sintered for 10 minutes in a muffle furnace set at 380 ° C. This operation was repeated twice, and one surface of the electrode was inactivated.

A film formed of two layers of a perfluorocarbon polymer (C polymer) having a terminal functional group of "-COOCH ₃ " and a perfluorocarbon polymer (S polymer) having a terminal group of "-SO ₂ F" was produced. The C polymer layer was 3 mils thick and the S polymer layer was 4 mils thick. The saponification process was performed to this two-layer film, and the ion exchanger was introduce | transduced by hydrolysis to the terminal of a polymer. The C polymer end was hydrolyzed to the carboxylic acid group and the S polymer end to the sulfo group. The ion exchange capacity as the sulfonic acid group was 1.0 meq / g, and the ion exchange capacity as the carboxylic acid group was 0.9 meq / g.

On the surface having a carboxylic acid group as an ion exchanger, the inactivated electrode surface was faced to heat press to integrate the ion exchange membrane and the electrode. Even after thermocompression bonding, one side of the electrode was exposed, and no part of the electrode penetrated the membrane.

Then, in order to suppress adhesion of the bubble which generate | occur | produces during electrolysis to the film | membrane, the perfluorocarbon polymer mixture in which zirconium oxide and a sulfo group were introduce | transduced was apply | coated on both surfaces. In this way, the membrane electrode assembly of Comparative Example 10 was produced.

Using the membrane electrode assembly, the force 1 applied per unit mass and unit area was measured. As a result, the electrode and the membrane were strongly joined by thermocompression bonding, and therefore the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed so as not to move, and when the electrode was pulled upward with a stronger force, a part of the membrane was torn when a force of 1.50 (N / mg · cm 2) was applied. The force 1 applied per unit mass and unit area of the membrane electrode assembly of Comparative Example 10 was at least 1.50 (N / mg · cm 2), and was strongly bonded.

When the cylindrical winding winding evaluation (1) was performed, the contact area with the plastic pipe was less than 5%. On the other hand, when the column winding winding evaluation (2) of diameter 280 mm was performed, the electrode and the membrane were 100% bonded, but the diaphragm was not wound up to the cylinder initially. The result of the 145 mm diameter cylindrical winding evaluation (3) was also the same. This result meant that the handling of the film was impaired by the integrated electrodes, making it difficult to wind or bend the rolls. Handling property had a problem with "3". Membrane damage evaluation was "0". Moreover, when electrolytic evaluation was performed, the voltage was high, the current efficiency was low, the salt concentration (50% conversion value) in caustic soda became high, and electrolytic performance worsened.

In addition, the thickness of the electrode was 114 micrometers. The thickness of the catalyst layer was 14 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 13 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2.

Comparative Example 11

In Comparative Example 11, a nickel mesh having a wire diameter of 150 µm, 40 mesh, a gauge thickness of 300 µm, and a porosity of 58% was used as the electrode substrate for cathode electrolysis. Other than that, the membrane electrode assembly was produced similarly to the comparative example 10.

Using the membrane electrode assembly, the force 1 applied per unit mass and unit area was measured. As a result, the electrode and the membrane were strongly joined by thermocompression bonding, and therefore the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed so as not to move, and when the electrode was pulled upward with a stronger force, a part of the membrane was torn when a force of 1.60 (N / mg · cm 2) was applied. The force 1 applied per unit mass and unit area of the membrane electrode assembly of Comparative Example 11 was at least 1.60 (N / mg · cm 2), and was strongly bonded.

The 280 mm-diameter cylindrical winding evaluation (1) was performed using this membrane electrode assembly, and the contact area with the plastic pipe was less than 5%. On the other hand, when the column winding winding evaluation (2) of diameter 280 mm was performed, the electrode and the membrane were 100% bonded, but the diaphragm was not wound up to the cylinder initially. The result of the 145 mm diameter cylindrical winding evaluation (3) was also the same. This result meant that the handling of the film was impaired by the integrated electrodes, making it difficult to wind or bend the rolls. Handling property had a problem with "3". Moreover, when electrolytic evaluation was performed, the voltage was high, the current efficiency was low, the salt concentration in caustic soda became high, and electrolytic performance worsened.

In addition, the thickness of the electrode was 308 micrometers. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 23 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2.

Comparative Example 12

(Preparation of Catalyst)

0.728 g of silver nitrate (Wako Pure Chemical Industries, Ltd.) and 1.86 g of cerium nitrate hexahydrate (Wako Pure Chemical Industries, Ltd.) were added to 150 ml of pure water to prepare an aqueous metal salt solution. 240 g of pure water was added to 100 g of an aqueous 15% tetramethylammonium hydroxide solution (Wako Pure Chemical Industries, Ltd.) to prepare an alkaline solution. While stirring the alkaline solution using a magnetic stirrer, the aqueous metal salt solution was added dropwise at 5 ml / min using a burette. The suspension containing the produced metal hydroxide fine particles was suction filtered, and then washed with water to remove alkali. Thereafter, the filtrate was transferred into 200 ml of 2-propanol (Kishida Chemical Co., Ltd.) and redispersed for 10 minutes with an ultrasonic disperser (US-600T, Nippon Seiki Co., Ltd.) to obtain a uniform suspension.

0.36 g of hydrophobic carbon black (Denka black (trademark) AB-7 (brand name), Denki Kagaku Kogyo Co., Ltd.), 0.84 g of hydrophilic carbon black (Ketjen black (trademark) EC-600JD (brand name), Mitsubishi Chemical Corporation) It was dispersed in 100 ml of 2-propanol and dispersed for 10 minutes by an ultrasonic disperser to obtain a suspension of carbon black. The suspension of the metal hydroxide precursor and the suspension of carbon black were mixed and dispersed for 10 minutes by an ultrasonic disperser. The suspension was suction filtered and dried at room temperature for half a day to obtain carbon black obtained by dispersing and fixing a metal hydroxide precursor. Subsequently, using an inert gas firing furnace (VMF165 type, Yamada Electric Co., Ltd.), firing was carried out at 400 ° C. for 1 hour in a nitrogen atmosphere to obtain carbon black A in which the electrode catalyst was dispersed and fixed.

(Powder making for reaction layer)

To 1.6 g of carbon black A in which the electrode catalyst was dispersed and immobilized, 0.84 ml of surfactant Triton (registered trademark) X-100 (trade name, ICN Biomedical) diluted with 20% by weight of pure water, and 15 ml of pure water were added to an ultrasonic disperser. Disperse for 10 minutes. 0.664 g of PTFE (polytetrafluoroethylene) dispersion (PTFE30J (trade name), Mitsui DuPont Florochemical Co., Ltd.) was added to this dispersion, followed by stirring for 5 minutes, followed by suction filtration. Furthermore, it dried at 80 degreeC in 1 hour for 1 hour, grind | pulverized with the mill, and obtained the powder A for reaction tanks.

(Production of Powder for Gas Diffusion Layer)

20 g of hydrophobic carbon black (Denka Black (registered trademark) AB-7 (trade name)), 50 ml of surfactant Triton (registered trademark) X-100 (brand name) diluted with 20% by weight of pure water, pure water 360 ml of ultrasonic disperser Dispersion was carried out for 10 minutes. 22.32 g of PTFE dispersion was added to the obtained dispersion, followed by stirring for 5 minutes, followed by filtration. Furthermore, it dried in 80 degreeC dryer for 1 hour, grind | pulverized by the mill, and obtained the powder A for gas diffusion layers.

(Production of Gas Diffusion Electrode)

8.7 ml of ethanol was added to 4 g of powder A for gas diffusion layers, and the mixture was kneaded to obtain a jelly type. This jelly-like gas diffusion layer powder was molded into a sheet by a roll forming machine, and a silver mesh (SW = 1, LW = 2, thickness = 0.3 mm) was embedded as a current collector and finally molded into a 1.8 mm sheet. . 2.2 ml of ethanol was added to 1 g of the powder A for the reaction layer, and kneaded to obtain a jelly type. The jelly-like reaction layer powder was molded into a sheet of 0.2 mm in thickness by a roll molding machine. Moreover, two sheets of the sheet | seat obtained using the produced powder A for gas diffusion layers, and the sheet | seat obtained using the powder A for reaction layers were laminated | stacked, and it shape | molded in the sheet shape of 1.8 mm with the roll molding machine. This laminated sheet was dried for one day only at room temperature, and ethanol was removed. In addition, in order to remove the remaining surfactant, pyrolysis treatment was performed at 300 ° C. for 1 hour in air. Wrapped with aluminum foil, hot press was performed at 360 degreeC and 50 kgf / cm <2> for 1 minute with the hot press machine (SA303 (brand name), Tester Industry Co., Ltd.), and the gas diffusion electrode was obtained. The thickness of the gas diffusion electrode was 412 μm.

Electrolytic evaluation was performed using the obtained electrode. The cross-sectional structure of the electrolytic cell is arranged in the order of the current collector, the mattress, the nickel mesh feeder, the electrode, the film, and the anode from the cathode chamber side to form a zero gap structure. The results are shown in Table 2.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 19 mm.

The ventilation resistance of the electrode was measured, and found to be 25.88 (kPa · s / m) under measurement condition 1.

Moreover, handling property had a problem with "3". Moreover, when electrolytic evaluation was performed, current efficiency was low, the salt concentration in caustic soda became high, and electrolytic performance fell remarkably. Membrane damage evaluation also had a problem with "3".

From these results, it was found that when the gas diffusion electrode obtained in Comparative Example 12 was used, the electrolytic performance was significantly deteriorated. In addition, damage was observed on almost the entire surface of the ion exchange membrane. This was considered to be due to the fact that NaOH generated at the electrode stayed at the interface between the electrode and the diaphragm and had a high concentration because the airflow resistance of the gas diffusion electrode of Comparative Example 12 was remarkably large.

Comparative Example 13

As an electrode base material for cathode electrolysis, a nickel wire having a gauge thickness of 150 µm was prepared. The roughening process by this nickel wire was performed. Since it is difficult to measure the surface roughness of a nickel wire, in Comparative Example 13, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was taken as the surface roughness of the nickel wire. The blasting was performed with the alumina of particle number 320. Arithmetic mean roughness Ra was 0.64 mu m.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. An application roll wound with rubber (Inoac Corporation, E-4088 (trade name), thickness 10 mm) made of foamed EPDM (ethylene propylene diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride); It was installed so that the coating liquid always contacted. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of one nickel wire produced in the comparative example 13 was 158 micrometers.

The nickel wire produced by the above method was cut to lengths of 110 mm and 95 mm. As shown in Fig. 16, the 110 mm nickel wire and the 95 mm nickel wire were vertically overlapped at the center of each nickel wire, and the intersection portion was bonded with an instantaneous adhesive (Aron Alpha®, Toa Synthetic Co., Ltd.). An electrode was produced. The electrode was evaluated and the results are shown in Table 2.

The electrode had the thickest portion where the nickel wire overlapped, and the electrode had a thickness of 306 µm. The thickness of the catalyst layer was 6 micrometers. The porosity was 99.7%.

The mass per unit area of the electrode was 0.5 (mg / cm 2). The force (1) and (2) applied per unit mass and unit area were all below the lower limit of the measurement of a tensile tester. For this reason, the result of the 280 mm diameter coil winding evaluation (1) was less than 5%, and the part from which an electrode and a diaphragm peeled off increased. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 15 mm.

The ventilation resistance of the electrode was measured and found to be 0.001 (kPa · s / m) or less under measurement condition 2. In measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring apparatus was measured as H (high), the ventilation resistance value was 0.0002 (kPa · s / m).

Moreover, using the structure shown in FIG. 17, an electrode (cathode) was provided on the Ni mesh feeder, and electrolysis evaluation was performed by the method as described in (9) Electrolysis evaluation. As a result, the voltage was as high as 3.16 V.

Comparative Example 14

In Comparative Example 14, using the electrode produced in Comparative Example 13, 110 mm nickel wire and 95 mm nickel wire were vertically overlapped at the center of each nickel wire as shown in FIG. The electrode was produced by adhering with an adhesive (Aron Alpha (registered trademark), Toa Synthetic Co., Ltd.). The electrode was evaluated and the results are shown in Table 2.

The electrode had the thickest portion where the nickel wire overlapped, and the electrode had a thickness of 306 µm. The thickness of the catalyst layer was 6 micrometers. The porosity was 99.4%.

The mass per unit area of the electrode was 0.9 (mg / cm 2). The force (1) and (2) applied per unit mass and unit area were all below the lower limit of the measurement of a tensile tester. For this reason, the result of the 280 mm diameter coil winding evaluation (1) was less than 5%, and the part from which an electrode and a diaphragm peeled off increased. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 16 mm.

The ventilation resistance of the electrode was measured and found to be 0.001 (kPa · s / m) or less under measurement condition 2. In measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring apparatus was measured as H (high), the ventilation resistance was 0.0004 (kPa · s / m).

Moreover, using the structure shown in FIG. 19, an electrode (cathode) was provided on the Ni mesh feeder, and electrolytic evaluation was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V.

Comparative Example 15

In Comparative Example 15, using the electrode produced in Comparative Example 13, 110 mm nickel wire and 95 mm nickel wire were vertically overlapped at the center of each nickel wire as shown in FIG. The electrode was produced by adhering with an adhesive (Aron Alpha (registered trademark), Toa Synthetic Co., Ltd.). The electrode was evaluated and the results are shown in Table 2.

The electrode had the thickest portion where the nickel wire overlapped, and the electrode had a thickness of 306 µm. The thickness of the catalyst layer was 6 µm. The porosity was 98.8%.

The mass per unit area of the electrode was 1.9 (mg / cm 2). The force (1) and (2) applied per unit mass and unit area were all below the lower limit of the measurement of a tensile tester. For this reason, the result of the 280 mm diameter coil winding evaluation (1) was less than 5%, and the part from which an electrode and a diaphragm peeled off increased. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 14 mm.

Moreover, when the ventilation resistance of the electrode was measured, it was 0.001 (kPa * s / m) or less in measurement condition 2. In measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring apparatus was measured as H (high), the ventilation resistance was 0.0005 (kPa · s / m).

Moreover, using the structure shown in FIG. 21, an electrode (cathode) was provided on the Ni mesh feeder, and electrolytic evaluation was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V.

TABLE 1

TABLE 2

In Table 2, before all the samples, the measurement of "force 1 per unit mass and unit area" and "force 2 per unit mass and unit area" was independent of the surface tension (i.e. flow Did not get off).

In Comparative Examples 1, 2 and 7 to 9, the mass per unit area was large, and the force 1 applied per unit mass and unit area was small, so that the adhesion to the diaphragm was poor. For this reason, when handling a diaphragm which is a polymer film, in a large electrolytic cell size (for example, 1.5 m in length and 3 m in width), it may always relax, and at this time, an electrode peels and cannot endure practical use.

In Comparative Examples 3 and 4, since the force 1 applied per unit mass and unit area was small, the adhesion to the diaphragm was poor. For this reason, when handling a diaphragm which is a polymer film, in a large electrolytic cell size (for example, 1.5 m in length and 3 m in width), it may always relax, and at this time, an electrode peels and cannot endure practical use.

The comparative examples 5 and 6 had large mass per unit area, and were bad in adhesiveness with a diaphragm. For this reason, when handling a diaphragm which is a polymer film, in a large electrolytic cell size (for example, 1.5 m in length and 3 m in width), it may always relax, and at this time, an electrode peels and cannot endure practical use.

In Comparative Examples 10 and 11, the film and the electrode were strongly joined by heat press, and therefore, they did not peel off from the film during handling as in Comparative Examples 1, 2 and 7-9. However, since it is strongly bonded to the electrode, the flexibility of the polymer film is lost, it is difficult to roll or bend in a roll shape, the handling properties are poor, and it is unbearable for practical use.

In Comparative Examples 10 and 11, the electrolytic performance was greatly deteriorated. The reason why the voltage greatly increased was considered to be that the flow of ions was inhibited by the state in which the electrode was embedded in the ion exchange membrane. The reason why the current efficiency is lowered and the salt concentration in the caustic soda is deteriorated is that the carboxylic acid layer in which thickness unevenness of the carboxylic acid layer occurs by embedding an electrode in a carboxylic acid layer having an effect of expressing high current efficiency and ion selectivity. Factors such as the penetration of electrodes embedded with a portion of the metal were considered.

In addition, in Comparative Examples 10 and 11, when a problem occurred in either of the diaphragm or the electrode, and replacement was necessary, it was strongly bonded, so it was impossible to replace only one side, resulting in high cost.

In Comparative Example 12, the electrolytic performance was greatly deteriorated. The reason why the voltage greatly increased was considered to be that the product remained at the interface between the membrane and the electrode.

In Comparative Examples 13-15, since the force (1) and (2) applied per unit mass and unit area were both small (below the lower limit of measurement), adhesiveness with a diaphragm was bad. For this reason, when handling a diaphragm which is a polymer film, in a large electrolytic cell size (for example, 1.5 m in length and 3 m in width), it may always relax, and at this time, an electrode peels and cannot endure practical use.

In the present embodiment, since the membrane and the electrode are in close contact with each other on the surface with a suitable force, there is no problem that the electrode is peeled off during handling, and since the flow of ions in the membrane is not impaired, good electrolytic performance is exhibited.

<Verification of Second Embodiment>

As described below, an experimental example corresponding to the second embodiment (hereinafter simply referred to as "an example" in the section of <verification of the second embodiment>) and an experimental example not corresponding to the second embodiment (Hereinafter, simply referred to as "comparative example" in the following section in <Verification of Second Embodiment>) were prepared, and these were evaluated by the following method. The detail is demonstrated, referring FIGS. 31-42 suitably.

〔Assessment Methods〕

(1) Opening rate

The electrode was cut out to a size of 130 mm x 100 mm. The average value which measured ten points of surface uniformly was computed using the dejimatic thickness gauge (Mitsutoyo Corporation make, minimum indication 0.001mm). The volume was computed using this as thickness of an electrode (gauge thickness). Then, the mass was measured by the electronic balance, and the porosity or the porosity was computed from the specific gravity of metal (specific gravity of nickel = 8.908 g / cm <3>, specific gravity of titanium = 4.506 g / cm <3>).

Porosity (porosity) (%) = (1- (electrode mass) / (electrode volume × specific gravity of metal)) × 100

(2) mass per unit area (mg / cm 2)

The electrode was cut out to a size of 130 mm x 100 mm, and the mass was measured by electronic balance. The mass per unit area was computed by dividing the value by area (130 mm x 100 mm).

(3) Force applied per unit mass and unit area (1) (adhesive force) (N / mg · cm 2)

[Method (i)]

A tensile compression tester was used for the measurement (Imada Co., Ltd., tester main body: SDT-52NA type tensile compression tester, weighting meter: SL-6001 type weighting machine).

The blast process was performed with the alumina of particle number 320 on the nickel plate of thickness 1.2mm and width-and-length 200mm. The arithmetic mean surface roughness Ra of the nickel plate after blasting was 0.7 micrometers. Here, the stylus type surface roughness measuring instrument SJ-310 (Mitsutoyo Co., Ltd.) was used for surface roughness measurement. The measurement sample was installed on the surface plate parallel to the ground, and the arithmetic mean roughness Ra was measured under the following measurement conditions. The measurement described the average value at the time of six implementations.

<Shape of the needle> Cone taper angle = 60 °, tip radius = 2 μm, static measuring force = 0.75 mN

<Roughness standard> JIS2001

<Evaluation curve> R

<Filter> GAUSS

<Cut-off value λc> 0.8 mm

<Cut off value λs> 2.5 μm

<Number of Sections> 5

<Jeonju, Huju> Yes

The nickel plate was fixed to the lower chuck of the tensile compression tester so as to be vertical.

As the diaphragm, the following ion exchange membrane A was used.

As a reinforcing core material, it was made of polytetrafluoroethylene (PTFE) and 90 denier monofilament was used (hereinafter referred to as PTFE company). As the sacrificial yarn, a yarn in which twisted polyethylene denephthalate (PET) of 35 deniers and 6 filaments was applied 200 times / m was used (hereinafter referred to as PET yarn). First, in each of the two directions of TD and MD, the woven fabric was plain so that two lines of PTFE yarn were disposed between 24 lines / inch and two sacrificed yarns were adjacent to adjacent PTFE yarns. The obtained woven fabric was crimped with a roll to obtain a woven fabric having a thickness of 70 µm.

Next, Resin A, CF ₂ = CF ₂ , a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ , having an ion exchange capacity of 0.85 mg equivalent / g. And Resin B of a dry resin having a copolymer of CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and having an ion exchange capacity of 1.03 mg equivalent / g.

Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 µm and a resin B layer of 104 µm was obtained by a coextrusion T die method.

Subsequently, a hot plate having a heating source and a vacuum source therein and having fine holes on its surface was laminated in the order of release paper (conical embossing having a height of 50 μm), reinforcing material and film X, and hot plate. After heating and pressure-reducing for 2 minutes on the conditions of surface temperature 223 degreeC, and the pressure reduction degree 0.067 MPa, the composite film was obtained by removing a release paper.

The obtained composite membrane was saponified by immersing for 20 minutes in 80 degreeC aqueous solution containing 30 mass% of dimethyl sulfoxide (DMSO), and 15 mass% of potassium hydroxide (KOH). Then, it was immersed in 50 degreeC aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour, the counter ion of the ion exchange group was substituted by Na, and it washed with water continuously. Furthermore, it dried at 60 degreeC.

Further, a suspension obtained by adding 20 mass% of zirconium oxide having a primary particle size of 1 μm to a 5 mass% ethanol solution of the acid-type resin of the resin B was dispersed, sprayed onto both surfaces of the composite membrane by a suspension spray method, and A coating was formed on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconium oxide was 0.5 mg / cm 2 as measured by fluorescence X-ray measurement. In addition, the average particle diameter was measured by the particle size distribution meter ("SALD (trademark) 2200" by Shimadzu Corporation).

The ion exchange membrane (diaphragm) obtained above was immersed in pure water for 12 hours or more, and used for the test. The nickel plate was sufficiently wetted with pure water and brought into contact with water under tension. At this time, it installed so that the position of the upper surface of a nickel plate and an ion exchange membrane may match.

The electrolytic electrode sample (electrode) used for the measurement was cut | disconnected to 130 mm long. Ion exchange membrane A was cut out to 170 mm in length and width. One side of the electrode was sandwiched between two stainless plates (1 mm in thickness, 9 mm in length, and 170 mm in width), and the stainless plate and the center of the electrode were aligned so as to be aligned, and then fixed evenly with four clips. The center of the stainless plate was fitted to the chuck above the tensile compression tester, and the electrodes were suspended. At this time, the load applied to the tester was 0N. First, the stainless plate, the electrode, and the clip assembly were removed from the tensile compression tester, and soaked in a batt containing pure water in order to sufficiently wet the electrode with pure water. After that, the center of the stainless steel plate was placed on the upper chuck of the tensile compression tester and the electrode was suspended.

The upper chuck of the tensile compression tester was lowered, and the electrolytic electrode sample was adhered to the surface of the ion exchange membrane by pure surface tension. The adhesive surface at this time was 130 mm in width and 110 mm in length. Pure water in the bottle was sprayed on the entire electrode and the ion exchange membrane, so that the diaphragm and the electrode were sufficiently wet again. Then, the roller which wound the EPDM sponge rubber of the independent foaming type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) was pressed lightly from the top of the electrode, and it rolled downwards from the top to remove the extra pure water. The roller was rolled only once.

Weight measurement was started by raising the electrode at a rate of 10 mm / min, and the weight when the overlapping portion of the electrode and the diaphragm became 130 mm in width and 100 mm in length was recorded. This measurement was performed three times and the average value was calculated.

This average value was divided by the area of the overlapped portion of the electrode and the ion exchange membrane and the electrode mass of the portion overlapped with the ion exchange membrane to calculate the force (1) applied per unit mass and unit area. The electrode mass of the part which overlapped with the ion exchange membrane was calculated | required by the proportional calculation from the value obtained from the mass per unit area (mg / cm <2>) of said (2).

The environment of the measurement room was 23 ± 2 ° C. and 30 ± 5% relative humidity.

In addition, when the electrode used by the Example and the comparative example was adhere | attached on the ion-exchange membrane adhered by the surface tension to the nickel plate fixed vertically, it adhered by self-supporting, without flowing down or peeling.

31, the schematic diagram of the evaluation method of the applied force 1 was shown.

In addition, the minimum of the measurement of the tensile tester was 0.01 (N).

(4) Force applied per unit mass and unit area (2) (adhesive force) (N / mg · cm 2)

[Method (ii)]

A tensile compression tester was used for the measurement (Imada Co., Ltd., tester main body: SDT-52NA type tensile compression tester, weighting meter: SL-6001 type weighting machine).

The same nickel plate as the method (i) was fixed to the lower chuck of the tensile compression tester so as to be vertical.

The electrolytic electrode sample (electrode) used for the measurement was cut | disconnected to 130 mm long. Ion exchange membrane A was cut out to 170 mm in length and width. One side of the electrode was sandwiched between two stainless plates (1 mm in thickness, 9 mm in length, and 170 mm in width), and the stainless plate and the center of the electrode were aligned so as to be aligned, and then fixed evenly with four clips. The center of the stainless plate was fitted to the chuck above the tensile compression tester, and the electrodes were suspended. At this time, the load applied to the tester was 0N. First, from the tensile compression tester, the stainless plate, the electrode, and the clip assembly were removed, and soaked in a batt containing pure water in order to sufficiently wet the electrode with pure water. Then, the center of the stainless plate was pinched again on the chuck | zipper of a tension compression tester, and the electrode was suspended.

The upper chuck of the tensile compression tester was lowered, and the electrolytic electrode sample was adhered to the nickel plate surface by the surface tension of the solution. The adhesive surface at this time was 130 mm in width and 110 mm in length. The pure water in the bottle was sprayed on the electrode and the whole of the nickel plate, and the nickel plate and the electrode were made sufficiently wet again. Then, the roller which wound the EPDM sponge rubber of the independent foaming type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) was pressed lightly from the top of the electrode, and was rolled from the top to the bottom, and the excess solution was removed. The roller was rolled only once.

Weight measurement was started by raising the electrode at a rate of 10 mm / min, and the weight when the overlapping portion in the longitudinal direction of the electrode and the nickel plate became 100 mm was recorded. This measurement was performed three times and the average value was calculated.

The average value was divided by the area of the overlapped portion of the electrode and the nickel plate and the electrode mass of the portion overlapped with the nickel plate to calculate the force 2 applied per unit mass and unit area. The electrode mass of the part which overlapped with the diaphragm was calculated | required by the proportional calculation from the value obtained from the mass per unit area (mg / cm <2>) of said (2).

In addition, the environment of the measurement chamber was 23 ± 2 ° C. and 30 ± 5% relative humidity.

In addition, when the electrode used by the Example and the comparative example was adhere | attached by the surface tension to the nickel plate fixed vertically, it adhered by self-supporting, without flowing down or peeling.

In addition, the minimum of the measurement of the tensile tester was 0.01 (N).

(5) 280 mm diameter cylindrical winding evaluation method (1) (%)

(Membrane and cylinder)

Evaluation method (1) was implemented in the following procedures.

The ion exchange membrane A (diaphragm) created in [Method (i)] was cut into a size of 170 mm in width and length. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. In Comparative Examples 1 and 2, since the electrode was integrated into the ion exchange membrane by heat press, an integrated body of the ion exchange membrane and the electrode was prepared (the electrode was 130 mm long). After the ion exchange membrane was sufficiently immersed in pure water, it was placed on the curved surface of a pipe made of plastic (polyethylene) having an outer diameter of 280 mm. Then, the excess solution was removed with the roller which wound the EPDM sponge rubber of the independent foaming type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm). The roller rolled the ion exchange membrane image toward the left side to the right side of the schematic diagram shown in FIG. The roller was rolled only once. After 1 minute, the ratio of the part where the ion exchange membrane and the pipe electrode made of plastic with an outer diameter of 280 mm were in close contact was measured.

(6) 280 mm diameter cylindrical winding evaluation method (2) (%)

(Membrane and electrode)

Evaluation method (2) was implemented in the following procedures.

The ion exchange membrane A (diaphragm) created in [Method (i)] was cut to a size of 170 mm in width and length, and the electrode was cut to 130 mm in width and length. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminated body was placed on the curved surface of the plastic (polyethylene) pipe of outer diameter 280 mm so that an electrode might become outer side. Subsequently, while pressing the roller which wound EPDM sponge rubber of the independent foaming type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) lightly from the top of an electrode, it rolls toward the right side from the left side of the schematic diagram shown in FIG. Removed. The roller was rolled only once. After 1 minute, the ratio of the part where the ion exchange membrane and the electrode were in close contact was measured.

(7) 145 mm diameter cylindrical winding evaluation method (3) (%)

(Membrane and electrode)

The evaluation method (3) was implemented in the following procedures.

The ion exchange membrane A (diaphragm) created in [Method (i)] was cut to a size of 170 mm in width and length, and the electrode was cut to 130 mm in width and length. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. The laminate was placed on the curved surface of a pipe made of plastic (polyethylene) having an outer diameter of 145 mm so that the electrode was outside. Subsequently, while pressing the roller which wound EPDM sponge rubber of independent foam type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) lightly from the top of an electrode, it rolls toward the right side from the left side of the schematic diagram shown in FIG. Removed. The roller was rolled only once. After 1 minute, the ratio of the part where the ion exchange membrane and the electrode were in close contact was measured.

(8) handling (response evaluation)

(A) The ion-exchange membrane A (diaphragm) created by [method (i)] was cut into the size of 170 mm horizontally and 95 x 110 mm. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. In each Example, the ion exchange membrane and the electrode were fully immersed in three kinds of solutions of sodium bicarbonate aqueous solution, 0.1N NaOH aqueous solution, and pure water, and were laminated and set on a Teflon plate. The distance between the positive electrode cell and the negative electrode cell used in the electrolytic evaluation was set to about 3 cm, the set laminate was lifted, and an operation of inserting and sandwiching the gap was performed. When this operation was performed, it was checked while operating whether the electrode was not twisted or dropped.

(B) The ion exchange membrane A (diaphragm) created in [Method (i)] was cut to a size of 170 mm in width and length, and the electrode was cut to 95 × 110 mm. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. In each Example, the ion exchange membrane and the electrode were fully immersed in three kinds of solutions of sodium bicarbonate aqueous solution, 0.1N NaOH aqueous solution, and pure water, and were laminated and set on a Teflon plate. The two adjacent corners of the membrane part of the laminated body were grasped by hand, and the laminated body was lifted up so that it was vertical. From this state, it moved so that the two edge | edges grasped | handed by hand might be made to become convex and concave. This was repeated once more to confirm the followability of the electrode to the film. The result was evaluated in four steps of 1-4 based on the following indicators.

1: Good handling

2: Handleable

3: difficult handling

4: almost impossible to handle

Here, about the sample of the comparative example 2-5, handling was carried out with the same size as the large electrolysis cell of the size of 1.3 m x 2.5 m and the ion exchange membrane of 1.5 m x 2.8 m with an electrode. The evaluation result ("3") of the comparative example 5 was made into the index which evaluates the difference at the time of making evaluation of said (A), (B), and large size. That is, when the result of evaluating a small laminated body is "1" and "2", even if it was set as the large size, it evaluated that there was no problem in handling property.

(9) Electrolytic evaluation (voltage (V), current efficiency (%), salt concentration in caustic soda (ppm, 50% equivalent))

The electrolytic performance was evaluated by the following electrolytic experiment.

A positive electrode cell (anode terminal cell) made of titanium having a positive electrode chamber provided with a positive electrode and a negative electrode cell having a negative electrode chamber (cathode terminal cell) made of nickel provided with a negative electrode were opposed to each other. A pair of gaskets were arrange | positioned between cells, and the laminated body (the laminated body of an ion exchange membrane A and an electrode for electrolysis) was sandwiched between a pair of gaskets. Then, an anode cell, a gasket, a laminate, a gasket, and a cathode were brought into close contact to obtain an electrolysis cell, and an electrolytic cell containing the same was prepared.

As an anode, it produced by apply | coating, drying, and baking the mixed solution of ruthenium chloride, iridium chloride, and titanium tetrachloride on the titanium base material which carried out the blast and acid etching process as a pretreatment. The anode was fixed to the anode chamber by welding. As the negative electrode, those described in Examples and Comparative Examples were used. Nickel expanded metal was used as an electrical power collector of a negative electrode chamber. The size of the current collector was 95 mm in length × 110 mm in width. As the metal elastic body, a mattress woven from nickel thin wire was used. The mattress, which is a metal elastomer, was placed on the current collector. A nickel wire having a diameter of 150 µm was covered with a flat nickel mesh having a size of 40 mesh, and four corners of the Ni mesh were fixed to a current collector with a string made of Teflon (registered trademark). This Ni mesh was used as a feeder. In this electrolytic cell, the repulsive force of the mattress which is a metal elastic body is used, and it has a zero gap structure. As the gasket, a rubber gasket made of EPDM (ethylene propylene diene) was used. As a diaphragm, the ion exchange membrane A (160 mm long) created by [method (i)] was used.

Salt electrolysis was performed using the said electrolysis cell. The brine concentration (sodium chloride concentration) of the anode chamber was adjusted to 205 g / L. The sodium hydroxide concentration of the cathode chamber was adjusted to 32 mass%. Each temperature of the anode chamber and the cathode chamber was adjusted such that the temperature in each electrolytic cell was 90 ° C. Salt electrolysis was performed at a current density of 6 kA / m 2, and the salt concentration in voltage, current efficiency, and caustic soda was measured. Here, the current efficiency is a ratio of the amount of generated caustic soda to the current that flows, and the current efficiency decreases when impurity ions or hydroxide ions, not sodium ions, move the ion exchange membrane by the current that flows. The current efficiency was obtained by dividing the number of moles of caustic soda generated at a given time by the number of moles of electrons of the current flowing therein. The number of moles of caustic soda was determined by recovering the caustic soda produced by electrolysis into a poly tank and measuring the mass thereof. The sodium chloride concentration in caustic soda represented the value converted from caustic soda to 50%.

Table 3 also shows the specifications of the electrode and the power feeder used in Examples and Comparative Examples.

(11) Measurement of the thickness of the catalyst layer, the electrode base for electrolysis, the thickness of the electrode

The thickness of the electrode base material for electrolysis computed the average value which measured 10 points uniformly in-plane using the dejimatic thickness gauge (Mitsutoyo Corporation make, minimum display 0.001mm). This was made into the thickness (gauge thickness) of the electrode base material for electrolysis. The thickness of the electrode computed the average value which measured 10 points uniformly in-plane with the dejimatic thickness gauge similarly to the electrode base material. This was made into the thickness (gauge thickness) of an electrode. The thickness of the catalyst layer was obtained by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

(12) elastic deformation test of electrode

The ion-exchange membrane A (diaphragm) and the electrode which were created by [method (i)] were cut | judged to the size of 110 mm width and height. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. After the laminate was fabricated by overlapping the ion exchange membrane and the electrode under a condition of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, as shown in FIG. Wound up. The wound laminate was fixed using a binding band made of polyethylene so as not to be peeled or relaxed from the PVC pipe. It kept in this state for 6 hours. Then, the binding band was removed and the laminated body was loosened from the pipe made from PVC. Only the electrode was placed on the surface plate, and the heights L ₁ and L ₂ of the portion floating from the surface plate were measured to obtain an average value. This value was used as an index of electrode deformation. That is, the smaller the value is, the harder it is to deform.

In addition, when using an expanded metal, when winding up, there are two types, SW direction and LW direction. In this test, it wound up to SW direction.

Moreover, about the softness after plastic deformation was evaluated about the electrode in which the deformation | transformation (electrode which did not return to the original flat state) was shown by FIG. That is, the electrode which had a deformation | transformation was placed on the diaphragm fully immersed in pure water, the one end was fixed, the opposing edge part which floated was pressed to the diaphragm, the force was opened, and it evaluated whether the electrode which a deformation | transformation followed the diaphragm.

(13) membrane damage evaluation

As the diaphragm, the following ion exchange membrane B was used.

As the reinforcing core material, polytetrafluoroethylene (PTFE), which was made into a yarn shape by applying a twist of 900 times / m to a 100 denier tape yarn (hereinafter referred to as PTFE company). As a sacrificial warp yarn, a yarn in which 35 denier and 8 filament polyethylene terephthalate (PET) was twisted 200 times / m was used (hereinafter referred to as PET yarn). As a weft sacrificial yarn, a yarn in which 35 denier and 8 filament polyethylene terephthalate (PET) was twisted 200 times / m was used. First, a PTFE woven fabric was plain weave so that two lines of 24 lines / inch and a sacrificial yarn were disposed between adjacent PTFE yarns to obtain a woven fabric having a thickness of 100 µm.

Next, CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ is a copolymer of dry resin with an ion exchange capacity of 0.92 mg equivalents / g (CF), CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F is a copolymer of a dry resin (B1) having an ion exchange capacity of 1.10 mg equivalent / g. Using these polymers (A1) and (B1), the two-layer film X having the thickness of the polymer (A1) layer of 25 µm and the polymer (B1) layer of 89 µm was obtained by the coextrusion T die method. In addition, the ion exchange capacity of each polymer showed the ion exchange capacity when the ion exchanger precursor of each polymer was hydrolyzed and converted into the ion exchanger.

In addition, separately prepared polymer (B2) of a dry resin having a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and having an ion exchange capacity of 1.10 mg equivalent / g. This polymer was single-layer extruded and the film Y of 20 micrometers was obtained.

Subsequently, on a hot plate having a heating source and a vacuum source therein and having micropores on the surface thereof, they were laminated in the order of the release paper, the film Y, the reinforcing material and the film X, and the hot plate temperature was 225 ° C. and the pressure reduction degree was 0.022 MPa. After heating and pressure-reducing for 2 minutes on conditions, the composite film was obtained by removing a release paper. The obtained composite membrane was saponified by immersion in an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) for 1 hour, and then immersed in 0.5 N NaOH for 1 hour to replace ions attached to the ion exchanger with Na. Continually washed. Furthermore, it dried at 60 degreeC.

In addition, hydrolyzed polymer (B3) of a dry resin having a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F, having an ion exchange capacity of 1.05 mg equivalent / g. After that, it was in acid form by hydrochloric acid. Zirconium oxide particles having an average particle diameter of 0.02 µm were prepared in a solution obtained by dissolving the polymer (B3 ') in the acid form in a 50/50 (mass ratio) mixture of water and ethanol at a ratio of 5% by mass. B3 ') and the mass ratio of zirconium oxide particle | grains were added so that it might be 20/80. Thereafter, the mixture was dispersed in a suspension of zirconium oxide particles in a ball mill to obtain a suspension.

This suspension was applied to both surfaces of the ion exchange membrane by the spray method and dried to obtain an ion exchange membrane B having a coating layer containing a polymer (B3 ') and zirconium oxide particles. It was 0.35 mg / cm <2> when the coating density of zirconium oxide was measured by the fluorescent X-ray measurement.

The positive electrode used the same thing as (9) electrolytic evaluation.

As the negative electrode, those described in Examples and Comparative Examples were used. The current collector, the mattress, and the electric power feeder of the negative electrode chamber used the same thing as (9) Electrolytic evaluation. In other words, the Ni mesh is used as the feeder, and the repulsive force of the mattress, which is a metal elastic body, is used to form a zero gap structure. The gasket also used the same thing as (9) electrolytic evaluation. An ion exchange membrane B prepared by the above method was used as the diaphragm. That is, the electrolytic cell similar to (9) was prepared except the sandwiching body of the ion exchange membrane B and the electrode for electrolysis was sandwiched between a pair of gaskets.

Salt electrolysis was performed using the said electrolysis cell. The brine concentration (sodium chloride concentration) of the anode chamber was adjusted to 205 g / L. The sodium hydroxide concentration of the cathode chamber was adjusted to 32 mass%. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell was 70 ° C. Salt electrolysis was performed at a current density of 8 kA / m 2. Electrolysis was stopped 12 hours after the start of the electrolysis, and the ion exchange membrane B was taken out and the damage state was observed.

"0" means no damage. "1-3" means that there is damage, and the larger the number, the greater the degree of damage.

(14) air resistance of the electrode

The air permeation resistance of the electrode was measured using the air permeability tester KES-F8 (trade name, Kato Tech Co., Ltd.). The unit of ventilation resistance value is kPa * s / m. The measurement was performed 5 times and the average value is shown in Table 4. The measurement was performed under the following two conditions. In addition, the temperature of the measurement chamber was 24 degreeC and the relative humidity was 32%.

ㆍ Measurement condition 1 (ventilation resistance 1)

Piston Speed: 0.2 cm / s

Aeration amount: 0.4 cc / ㎠ / s

Measuring range: SENSE L (low)

Sample size: 50 mm x 50 mm

ㆍ Measurement condition 2 (ventilation resistance 2)

Piston Speed: 2 cm / s

Aeration amount: 4 cc / ㎠ / s

Measuring range: SENSE M (medium) or H (high)

Sample size: 50 mm x 50 mm

Example 2-1

As an electrode base material for negative electrode electrolysis, the electrolytic nickel foil whose gauge thickness is 16 micrometers was prepared. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. Arithmetic mean roughness Ra of the roughened surface was 0.71 micrometer. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted.

A circular hole was drilled into this nickel foil by punching to obtain a porous foil. Opening rate was 49%.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of the electrode produced in Example 2-1 was 24 µm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side. In addition, it is the total thickness of ruthenium oxide and cerium oxide.

Table 4 shows the measurement results of the adhesive force of the electrode produced by the above method. Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2.

The electrode produced by the above method was cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode is made to face the position near the center of the carboxylic acid layer side of the ion exchange membrane A (size is 160 mm x 160 mm) produced by 0.1N NaOH aqueous solution equilibrated, It adhered by the surface tension of aqueous solution.

Even when the four corners of the membrane portion of the membrane-integrated electrode in which the membrane and the electrode were integrated were held, and the electrode was placed on the ground side and the membrane-integrated electrode was suspended to be parallel to the ground, the electrodes did not peel off or fall off. In addition, even when the both ends of one side were held and the membrane-integrated electrode was suspended so as to be perpendicular to the ground, the electrode did not peel off or fall off.

The membrane-integrated electrode was sandwiched between the anode cell and the cathode cell such that the surface on which the electrode was attached was the cathode chamber side. The cross-sectional structure forms a zero-gap structure from the cathode chamber side in the order of a current collector, a mattress, a nickel mesh feeder, an electrode, a film, and an anode.

Electrolytic evaluation was performed about the obtained electrode. The results are shown in Table 4.

It showed low voltage, high current efficiency and low caustic concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF (fluorescence X-ray analysis), the roughened surface remained almost 100% of the coating, and the non-roughened surface reduced the coating. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 2-2

In Example 2-2, the electrolytic nickel foil whose gauge thickness is 22 micrometers was used as an electrode base material for negative electrode electrolysis. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. The arithmetic mean roughness Ra of the roughened surface was 0.96 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. The porosity was 44%. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 29 μm. The thickness of the catalyst layer was 7 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode. The coating was also formed on the unroughened side.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0033 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF, the roughened surface remained almost 100% of the coating, and the non-roughened surface reduced the coating. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 2-3

In Example 2-3, an electrolytic nickel foil having a gauge thickness of 30 µm was used as the electrode substrate for negative electrode electrolysis. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. The arithmetic mean roughness Ra of the roughened surface was 1.38 m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. The porosity was 44%. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 38 μm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF, the roughened surface remained almost 100% of the coating, and the non-roughened surface reduced the coating. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 2-4

In Example 2-4, electrolytic nickel foil having a gauge thickness of 16 µm was used as the electrode substrate for negative electrode electrolysis. One surface of this nickel foil was roughened by electrolytic nickel plating. Arithmetic mean roughness Ra of the roughened surface was 0.71 micrometer. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. The porosity was 75%. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 24 μm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF, the roughened surface remained almost 100% of the coating, and the non-roughened surface reduced the coating. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 2-5

Example 2-5 prepared the electrolytic nickel foil whose gauge thickness is 20 micrometers as an electrode base material for negative electrode electrolysis. Both surfaces of this nickel foil were roughened by electrolytic nickel plating. The arithmetic mean roughness Ra of the roughened surface was 0.96 mu m. Both sides had the same roughness. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Opening rate was 49%. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 30 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after the electrolysis was measured by XRF, almost 100% of the coating remained on both sides. When compared with Examples 2-1 to 2-4, the opposite side not facing the film indicates that good electrolytic performance can be exhibited even if there is little or no coating.

Example 2-6

Example 2-6 evaluated similarly to Example 2-1 except having performed coating to the electrode base material for negative electrode electrolysis by ion plating, and the result was shown in Table 4. In addition, ion plating formed into a film at the film-forming pressure of 7x10 <^-2> Pa in argon / oxygen atmosphere using the heating temperature of 200 degreeC and Ru metal target. The coating formed was ruthenium oxide.

The thickness of the electrode was 26 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-7

In Example 2-7, the electrode base material for negative electrode electrolysis was created by the electroforming method. The shape of the photomask was made into the shape which arranged the square of 0.485 mm x 0.485 mm lengthwise and horizontally at 0.15 mm space | interval. By performing exposure, image development, and electroplating in order, the nickel porous foil with a gauge thickness of 20 micrometers and a porosity of 56% was obtained. Arithmetic mean roughness Ra of the surface was 0.71 m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 37 μm. The thickness of the catalyst layer was 17 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-8

Example 2-8 was created by the electroforming method as an electrode base material for cathode electrolysis, and the gauge thickness was 50 µm and the porosity was 56%. Arithmetic mean roughness Ra of the surface was 0.73 m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 60 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-9

In Example 2-9, a nickel nonwoven fabric (manufactured by Nico Techno Co., Ltd.) having a gauge thickness of 150 µm and a porosity of 76% was used as the electrode base material for cathode electrolysis. Nickel fiber diameter of the nonwoven fabric was about 40 micrometers, and basis weight was 300 g / m <2>. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 165 mu m. The thickness of the catalyst layer was 15 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 29 mm, and did not return to the original flat state. Therefore, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastic deformation was carried out, it was confirmed that the diaphragm could be contacted with a small force, and this electrode was found to have good handling property.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0612 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was good as "0".

Example 2-10

In Example 2-10, a nickel nonwoven fabric (manufactured by Nico Techno Co., Ltd.) having a gauge thickness of 200 µm and a porosity of 72% was used as the electrode substrate for cathode electrolysis. The nickel fiber diameter of the nonwoven fabric was about 40 micrometers, and basis weight was 500 g / m <2>. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 215 탆. The thickness of the catalyst layer was 15 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

Bar subjected to transformation test of the electrodes, the average value of L _1, L ₂ is 40 mm, it did not go back up to the original flat state. Therefore, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastic deformation was carried out, it was confirmed that the diaphragm could be contacted with a small force, and this electrode was found to have good handling property.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0164 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was good as "0".

Example 2-11

In Example 2-11, foamed nickel (manufactured by Mitsubishi Material Co., Ltd.) having a gauge thickness of 200 µm and a porosity of 72% was used as the electrode substrate for cathode electrolysis. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

In addition, the thickness of the electrode was 210 micrometers. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 17 mm and it did not return to the original flat state. Therefore, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastic deformation was carried out, it was confirmed that the diaphragm could be contacted with a small force, and this electrode was found to have good handling property.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0402 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was good as "0".

[Example 2-12]

In Example 2-12, a nickel mesh having a wire diameter of 50 µm, 200 mesh, a gauge thickness of 100 µm, and a porosity of 37% was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. Even if blasting was performed, the porosity did not change. Since it is difficult to measure the roughness of the wire mesh surface, in Example 2-12, at the time of blasting, the nickel plate of thickness 1mm was blasted simultaneously, and the surface roughness of the nickel plate was made into the surface roughness of the wire mesh. The arithmetic mean roughness Ra of one wire mesh was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 110 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0.5 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0154 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-13

In Example 2-13, a nickel mesh having a wire diameter of 65 µm, 150 mesh, a gauge thickness of 130 µm, and a porosity of 38% was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. Even if blasting was performed, the porosity did not change. Since it is difficult to measure the roughness of the wire mesh surface, in Example 2-13, the nickel plate of thickness 1mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was made into the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.66 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, the said evaluation was performed like Example 2-1, and the result was shown in Table 4.

The thickness of the electrode was 133 mu m. The thickness of the catalyst layer was 3 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 6.5 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0124 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was also good at "0".

Example 2-14

In Example 2-14, the same substrate (gauge thickness 30 µm, porosity 44%) as in Example 2-3 was used as the electrode substrate for negative electrode electrolysis. The electrolytic evaluation was performed with the structure similar to Example 2-1 except not having provided the nickel mesh feed material. That is, the cross-sectional structure of the cell forms a zero-gap structure from the cathode chamber side in the order of the current collector, the mattress, the film integrated electrode, and the anode, and the mattress functions as a power feeder. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-15

In Example 2-15, the same substrate (gauge thickness 30 µm, porosity 44%) as in Example 2-3 was used as the electrode substrate for cathode electrolysis. In place of the nickel mesh feeder, a negative electrode having a deteriorated and high electrolytic voltage used in Reference Example 1 was provided. Other than that, electrolytic evaluation was performed by the same structure as Example 2-1. That is, the cross-sectional structure of the cell is arranged in the order of the current collector, the mattress, and the negative electrode (functioning as a power feeder), the electrode for electrolysis (cathode), the diaphragm, and the positive electrode deteriorated from the cathode chamber side in order of zero gap structure. And the cathode whose deterioration has increased the electrolytic voltage functions as a feeder. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-16

As an electrode base material for positive electrode electrolysis, titanium foil whose gauge thickness is 20 micrometers was prepared. The roughening process was given to both surfaces of the titanium foil. The titanium foil was punched out, and a circular hole was drilled into a porous foil. The diameter of the hole was 1 mm and the porosity was 14%. Arithmetic mean roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. Ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L, iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) with a iridium concentration of 100 g / L, titanium tetrachloride (Wakkoyaku Industry Co., Ltd.), ruthenium element and iridium It mixed so that the molar ratio of an element and a titanium element might be 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred to prepare a positive electrode coating solution.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). After apply | coating the said coating liquid to titanium porous foil, it dried for 10 minutes at 60 degreeC, and baked for 10 minutes at 475 degreeC. After repeating these series of application | coating, drying, plasticity, and baking a series of operations, it baked at 520 degreeC for 1 hour.

The electrode produced by the above method was cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The ion exchange membrane A (size: 160 mm x 160 mm) prepared in [Method (i)] equilibrated with 0.1 N NaOH aqueous solution was brought into close contact with the surface tension of the aqueous solution at a position near the center of the sulfonic acid layer side.

The negative electrode was prepared in the following order. First, a nickel wire mesh of 150 µm in diameter and 40 mesh was prepared as a substrate. After performing blasting with alumina as pretreatment, it was immersed in 6N hydrochloric acid for 5 minutes, and it fully wash | cleaned and dried with pure water.

Next, a ruthenium chloride solution (Tanaka Precious Metal Industry Co., Ltd.) and cerium chloride (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Then, drying for 10 minutes at 50 degreeC, plasticity for 3 minutes at 300 degreeC, and baking for 10 minutes at 550 degreeC was performed. Then, baking was performed at 550 degreeC for 1 hour. A series of operations of these coating, drying, plasticity, and baking were repeated.

Nickel expanded metal was used as an electrical power collector of a negative electrode chamber. The size of the current collector was 95 mm in length × 110 mm in width. As the metal elastic body, a mattress woven from nickel thin wire was used. The mattress, which is a metal elastomer, was placed on the current collector. The negative electrode created by the above method was covered thereon, and four corners of the mesh were fixed to the current collector with a string made of Teflon (registered trademark).

Even if the four edges of the membrane portion of the membrane-integrated electrode in which the membrane and the anode were integrated were held, and the electrode was brought to the ground side and the membrane-integrated electrode was suspended so as to be parallel to the ground, the electrodes did not peel off or twisted. In addition, even when the both ends of one side were held and the membrane-integrated electrode was suspended so as to be perpendicular to the ground, the electrode did not peel off or fall off.

The positive electrode, which had been used in Reference Example 3, had a deteriorated and high electrolytic voltage fixed by welding, and the membrane-integrated electrode was sandwiched between the positive electrode cell and the negative electrode so that the surface on which the electrode was attached was on the positive electrode side. That is, the cross-sectional structure of the cell was arranged from the cathode chamber side in the order of the current collector, the mattress, the cathode, the diaphragm, the electrolytic electrode (titanium porous foil anode), and the anode deteriorated to increase the electrolytic voltage to form a zero gap structure. The positive electrode which deteriorated and the electrolytic voltage became high functioned as a power feeder. In addition, between the titanium porous foil anode and the anode which deteriorated and the electrolytic voltage became high, it was only physically contacting and was not fixed by welding.

Evaluation was performed in this configuration in the same manner as in Example 2-1, and the results are shown in Table 4.

The thickness of the electrode was 26 μm. The thickness of the catalyst layer was 6 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 4 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0060 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-17

In Example 2-17, titanium foil having a gauge thickness of 20 μm and a porosity of 30% was used as the electrode substrate for positive electrode electrolysis. Arithmetic mean roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-16, and showed the result in Table 4.

The thickness of the electrode was 30 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 5 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0030 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-18

In Example 2-18, titanium foil having a gauge thickness of 20 μm and a porosity of 42% was used as the electrode substrate for positive electrode electrolysis. Arithmetic mean roughness Ra of the surface was 0.38 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-16, and showed the result in Table 4.

The thickness of the electrode was 32 mu m. The thickness of the catalyst layer was 12 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 2.5 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0022 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-19

In Example 2-19, titanium foil having a gauge thickness of 50 µm and a porosity of 47% was used as the electrode substrate for positive electrode electrolysis. Arithmetic mean roughness Ra of the surface was 0.40 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-16, and showed the result in Table 4.

The thickness of the electrode was 69 μm. The thickness of the catalyst layer was 19 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation test of the electrode was conducted, the average value of L ₁ and L ₂ was 8 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0024 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-20

In Example 2-20, a titanium nonwoven fabric having a gauge thickness of 100 µm, a titanium fiber diameter of about 20 µm, a basis weight of 100 g / m 2, and a porosity of 78% was used as the electrode substrate for anode electrolysis. Other than that, it evaluated similarly to Example 2-16, and showed the result in Table 4.

The thickness of the electrode was 114 탆. The thickness of the catalyst layer was 14 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 2 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0228 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-21

In Example 2-21, a titanium wire mesh having a gauge thickness of 120 μm, a titanium fiber diameter of about 60 μm, and 150 mesh was used as the electrode substrate for positive electrode electrolysis. The porosity was 42%. The blasting was performed with the alumina of particle number 320. Since it is difficult to measure the roughness of the wire mesh surface, in Example 2-21, the titanium plate of thickness 1mm was blasted simultaneously at the time of blasting, and the surface roughness of the titanium plate was made into the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.60 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-16, and showed the result in Table 4.

The thickness of the electrode was 140 μm. The thickness of the catalyst layer was 20 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 10 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0132 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 2-22

In Example 2-22, a positive electrode was used as the positive electrode feeder in the same manner as in Example 2-16, and the same titanium nonwoven fabric as in Example 2-20 was used as the positive electrode. As the negative electrode feeder, a negative electrode having a deteriorated and high electrolytic voltage was used in the same manner as in Example 2-15, and the same nickel foil electrode as in Example 2-3 was used as the negative electrode. The cross-sectional structure of the cell is arranged in the order of the current collector, the mattress, the deteriorated high voltage cathode, the nickel porous foil cathode, the diaphragm, the titanium nonwoven anode, and the deteriorated positive electrode voltage from the cathode chamber side to form a zero gap structure. The negative electrode and the positive electrode which are deteriorated and the electrolytic voltage increased are functioning as a power feeder. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode (anode) was 114 μm, and the thickness of the catalyst layer was 14 μm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode (anode). The thickness of the electrode (cathode) was 38 μm, and the thickness of the catalyst layer was 8 μm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode (cathode).

Sufficient adhesion was observed for both the positive and negative electrodes.

When the deformation test of the electrode (anode) was performed, the average value of L ₁ and L ₂ was 2 mm. When the deformation test of the electrode (cathode) was conducted, the average value of L ₁ and L ₂ was 0 mm.

The ventilation resistance of the electrode (anode) was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0228 (kPa · s / m) under measurement condition 2. The ventilation resistance of the electrode (cathode) was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". Film damage evaluation of both the positive electrode and the negative electrode was also good as "0". In Example 2-22, the negative electrode was stuck to one side of the diaphragm and the positive electrode was stuck to the opposite side, and the film damage evaluation was performed by combining the negative electrode and the positive electrode.

Example 2-23

In Example 2-23, a microporous membrane "Zirfon Perl UTP 500" manufactured by Agfa Corporation was used.

Zirfon membrane was used for the test after immersion in pure water for more than 12 hours. Otherwise, the said evaluation was performed similarly to Example 2-3, and the result was shown in Table 4.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

As in the case where the ion exchange membrane was used as the diaphragm, sufficient adhesive force was observed, the microporous membrane and the electrode were in close contact with each other by the surface tension, and the handling property was "1".

Example 2-24

As an electrode base material for negative electrode electrolysis, carbon cloth woven of carbon fibers having a gauge thickness of 566 µm was prepared. The coating liquid for forming an electrode catalyst in this carbon cloth was prepared in the following procedure. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. An application roll wound with rubber (Inoac Corporation, E-4088 (trade name), thickness 10 mm) made of foamed EPDM (ethylene propylene diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride); It was installed so that the coating liquid always contacted. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of the produced electrode was 570 micrometers. The thickness of the catalyst layer was 4 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode. The thickness of the catalyst layer was the total thickness of ruthenium oxide and cerium oxide.

Electrolytic evaluation was performed about the obtained electrode. The results are shown in Table 4.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm.

The ventilation resistance of the electrode was measured, and found to be 0.19 (kPa · s / m) under measurement condition 1 and 0.176 (kPa · s / m) under measurement condition 2.

In addition, handling property was "2", and it was judged that it was handleable as a large laminated body.

The voltage was high, the film damage evaluation was "1", and the film damage was confirmed. This was considered to be because the NaOH generated at the electrode stayed at the interface between the electrode and the diaphragm and became high due to the large airflow resistance of the electrode of Example 2-24.

Reference Example 1

In Reference Example 1, a cathode used in a large electrolytic cell for eight years as a cathode and deteriorated to increase the electrolytic voltage was used. The negative electrode was placed on the mattress of the negative electrode chamber in place of the nickel mesh feeder, and the electrolytic evaluation was performed by sandwiching the ion exchange membrane A prepared in [Method (i)]. In Reference Example 1, the membrane-integrated electrode was not used, and the cross-sectional structure of the cell was formed from the cathode chamber side by arranging a current collector, a mattress, and a cathode, an ion exchange membrane A, and an anode deteriorated to increase the electrolytic voltage to form a zero gap structure. I was.

As a result of the electrolytic evaluation by this structure, the voltage was 3.04V, the current efficiency was 97.0%, and the salt concentration (50% conversion value) in caustic soda was 20 ppm. Since the cathode deteriorated, the result was a high voltage.

Reference Example 2

In Reference Example 2, a nickel mesh feeder was used as the cathode. That is, electrolysis was performed by the nickel mesh which was not catalyst coated.

A nickel mesh negative electrode was provided on the mattress of the negative electrode chamber, and the electrolytic evaluation was performed through the ion exchange membrane A created in [method (i)]. The cross-sectional structure of the electric cell of Reference Example 2 was arranged in the order of the current collector, the mattress, the nickel mesh, the ion exchange membrane A, and the anode from the cathode chamber side to form a zero gap structure.

As a result of electrolytic evaluation by this structure, the voltage was 3.38V, the current efficiency was 97.7%, and the salt concentration (50% conversion value) in caustic soda was 24 ppm. Since the negative catalyst was not coated, the result was a high voltage.

Reference Example 3

In Reference Example 3, a positive electrode used in a large electrolytic cell for about 8 years as a positive electrode and having a deteriorated electrolytic voltage was used.

The cross-sectional structure of the electrolytic cell of Reference Example 3 is arranged from the cathode chamber side in the order of the current collector, the mattress, the cathode, and the ion exchange membrane A prepared in [Method (i)], and the anode deteriorated to increase the electrolytic voltage. Formed.

As a result of the electrolytic evaluation by this structure, the voltage was 3.18V, the current efficiency was 97.0%, and the salt concentration (50% conversion value) in caustic soda was 22 ppm. Since the anode deteriorated, the result was a high voltage.

Example 2-25

In Example 2-25, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 33% after pull roll processing was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 2-25, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was made the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.68 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 114 탆. The thickness of the catalyst layer was 14 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 67.5 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.05 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) was 64%, and the result of the 145 mm cylindrical coil winding evaluation (3) was 22%, and the part from which an electrode and a diaphragm peeled was increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 13 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2.

Example 2-26

In Example 2-26, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 16% after pull roll processing was used as the electrode substrate for negative electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 2-26, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was made the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 107 탆. The thickness of the catalyst layer was 7 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

The mass per unit area was 78.1 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.04 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) was 37%, and the result of the 145 mm cylindrical coil winding evaluation (3) was 25%, and the part from which an electrode and a diaphragm peeled off increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 18.5 mm. When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0176 (kPa · s / m) under measurement condition 2.

Example 2-27

In Example 2-27, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 40% after pull roll processing was used as the electrode substrate for negative electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 2-27, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.70 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Coating on the electrode base for electrolysis was performed by the same ion plating as Example 2-6. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 110 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The force 1 applied per unit mass and unit area was a small value of 0.07 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is 80%, and the result of the 145 mm cylindrical coil winding evaluation (3) is 32%, and the part from which an electrode and a diaphragm peeled off increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 11 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0030 (kPa · s / m) under measurement condition 2.

Example 2-28

In Example 2-28, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 58% after pull roll processing was used as an electrode base material for negative electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 2-28, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 109 탆. The thickness of the catalyst layer was 9 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

The force 1 applied per unit mass and unit area was a small value of 0.06 (N / mg · cm 2). For this reason, the result of the cylindrical winding evaluation 2 of 280 mm diameter was 69%, and the result of the cylindrical winding evaluation 3 of 145 mm diameter was 39%, and the part from which an electrode and a diaphragm peeled off increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 11.5 mm.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2.

Example 2-29

In Example 2-29, a nickel wire mesh having a gauge thickness of 300 µm and a porosity of 56% was used as the electrode substrate for cathode electrolysis. Since it is difficult to measure the surface roughness of the wire mesh, in Example 2-29, a nickel plate having a thickness of 1 mm was simultaneously blasted at the time of blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Arithmetic mean roughness Ra was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-1, and showed the result in Table 4.

The thickness of the electrode was 308 mu m. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 49.2 (mg / cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation 2 was 88%, and the result of the 145 mm cylindrical coil winding evaluation 3 was 42%, and the part from which an electrode and a diaphragm peeled off increased. This is easy when the electrode is peeled off when handling the film-integrated electrode, and the electrode peels off from the film and falls during handling. There is a problem in handling property as "3". It actually operated in large size and evaluated as "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 23 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2.

Example 2-30

In Example 2-30, a nickel wire mesh having a gauge thickness of 200 µm and a porosity of 37% was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of a wire mesh, in Example 2-30, the nickel plate of thickness 1mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was made into the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.65 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, adhesiveness was performed similarly to Example 2-1 as a result of electrode electrolysis evaluation and the measurement of adhesive force. The results are shown in Table 4.

The thickness of the electrode was 210 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 56.4 mg / cm 2. For this reason, the adhesiveness of an electrode and a diaphragm was bad in 63% of the result of the 145 mm diameter coil winding evaluation method (3). This is easy when the electrode is peeled off when handling the film-integrated electrode, and the electrode peels off from the film and falls during handling. There is a problem in handling property as "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 19 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0096 (kPa · s / m) under measurement condition 2.

Example 2-31

In Example 2-31, titanium expanded metal having a gauge thickness of 500 µm and a porosity of 17% after pull roll processing was used as the electrode substrate for positive electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 2-31, a titanium plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.60 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 2-16, and showed the result in Table 4.

In addition, the thickness of the electrode was 508 micrometers. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 152.5 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.01 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is less than 5%, and the result of the 145 mm cylindrical coil winding evaluation (3) is less than 5%, and the part from which an electrode and a diaphragm peeled off increased. When handling the membrane-integrated electrode, the electrode was likely to be peeled off, and during the handling, the electrode was peeled off from the film and fell. Handling property also had a problem with "4". Membrane damage evaluation was "0".

Bar subjected to transformation test of the electrode, the electrode is not to be recalled while dried in the form of a PVC pipe, it could not measure the value of L _1, L _2.

The ventilation resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0072 (kPa · s / m) under measurement condition 2.

Example 2-32

In Example 2-32, titanium expanded metal having a gauge thickness of 800 µm and a porosity of 8% after pull roll processing was used as the electrode substrate for positive electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 2-32, a titanium plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.61 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, the said evaluation was performed similarly to Example 2-16, and the result was shown in Table 4.

The thickness of the electrode was 808 μm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 251.3 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.01 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is less than 5%, and the result of the 145 mm cylindrical coil winding evaluation (3) is less than 5%, and the part from which an electrode and a diaphragm peeled off increased. When handling the membrane-integrated electrode, the electrode was likely to be peeled off, and during the handling, the electrode was peeled off from the film and fell. Handling property also had a problem with "4". Membrane damage evaluation was "0".

Bar subjected to transformation test of the electrode, the electrode is not to be recalled while dried in the form of a PVC pipe, it could not measure the value of L _1, L _2.

The ventilation resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0172 (kPa · s / m) under measurement condition 2.

Example 2-33

In Example 2-33, titanium expanded metal having a gauge thickness of 1000 µm and a porosity of 46% after pull roll processing was used as the electrode substrate for positive electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 2-33, a titanium plate having a thickness of 1 mm was simultaneously blasted at the time of blasting, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.59 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, the said evaluation was performed similarly to Example 2-16, and the result was shown in Table 4.

In addition, the thickness of the electrode was 1011 micrometers. The thickness of the catalyst layer was 11 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 245.5 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.01 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is less than 5%, and the result of the 145 mm cylindrical coil winding evaluation (3) is less than 5%, and the part from which an electrode and a diaphragm peeled off increased. When handling the membrane-integrated electrode, the electrode was likely to be peeled off, and during the handling, the electrode was peeled off from the film and fell. Handling property also had a problem with "4". Membrane damage evaluation was "0".

Bar subjected to transformation test of the electrode, the electrode is not to be recalled while dried in the form of a PVC pipe, it could not measure the value of L _1, L _2.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

Example 2-34

As an electrode base material for cathode electrolysis, a nickel wire having a gauge thickness of 150 µm was prepared. The roughening process by this nickel wire was performed. Since it is difficult to measure the surface roughness of a nickel wire, in Example 2-34, the nickel plate of thickness 1mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was made into the surface roughness of the nickel wire. The blasting was performed with the alumina of particle number 320. Arithmetic mean roughness Ra was 0.64 mu m.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. An application roll wound with rubber (Inoac Corporation, E-4088 (trade name), thickness 10 mm) made of foamed EPDM (ethylene propylene diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride); It was installed so that the coating liquid always contacted. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of one nickel wire produced in Example 2-34 was 158 micrometers.

The nickel wire produced by the above method was cut to lengths of 110 mm and 95 mm. As shown in Fig. 37, the 110 mm nickel wire and the 95 mm nickel wire were vertically overlapped at the center of each nickel wire, and the intersection portion was bonded with an instantaneous adhesive (Aron Alpha®, Toa Synthetic Co., Ltd.). An electrode was produced. The electrode was evaluated, and the results are shown in Table 4.

The electrode had the thickest portion where the nickel wire overlapped, and the electrode had a thickness of 306 µm. The thickness of the catalyst layer was 6 µm. The porosity was 99.7%.

The mass per unit area of the electrode was 0.5 (mg / cm 2). The force (1) and (2) applied per unit mass and unit area were all below the lower limit of the measurement of a tensile tester. For this reason, the result of the 280 mm diameter coil winding evaluation (1) was less than 5%, and the part from which an electrode and a diaphragm peeled off increased. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 15 mm.

The ventilation resistance of the electrode was measured and found to be 0.001 (kPa · s / m) or less under measurement condition 2. In measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring apparatus was measured as H (high), the ventilation resistance value was 0.0002 (kPa · s / m).

Moreover, using the structure shown in FIG. 38, an electrode (cathode) was provided on the Ni mesh feeder, and electrolysis evaluation was performed by the method as described in (9) Electrolysis evaluation. As a result, the voltage was as high as 3.16 V.

Example 2-35

In Example 2-35, using the electrode produced in Example 2-34, as shown in FIG. 39, the 110 mm nickel wire and the 95 mm nickel wire were vertically overlapped at the center of each nickel wire, The intersection portion was bonded with an instantaneous adhesive (Aron Alpha (registered trademark), Toa Synthetic Co., Ltd.) to prepare an electrode. The electrode was evaluated, and the results are shown in Table 4.

The electrode had the thickest portion where the nickel wire overlapped, and the electrode had a thickness of 306 µm. The thickness of the catalyst layer was 6 µm. The porosity was 99.4%.

The mass per unit area of the electrode was 0.9 (mg / cm 2). The force (1) and (2) applied per unit mass and unit area were all below the lower limit of the measurement of a tensile tester. For this reason, the result of the 280 mm diameter coil winding evaluation (1) was less than 5%, and the part from which an electrode and a diaphragm peeled off increased. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 16 mm.

The ventilation resistance of the electrode was measured and found to be 0.001 (kPa · s / m) or less under measurement condition 2. In measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring apparatus was measured as H (high), the ventilation resistance was 0.0004 (kPa · s / m).

In addition, using the structure shown in FIG. 40, an electrode (cathode) was provided on the Ni mesh feeder, and electrolytic evaluation was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V.

Example 2-36

In Example 2-36, using the electrode produced in Example 2-34, as shown in Fig. 41, the 110 mm nickel wire and the 95 mm nickel wire were vertically overlapped at the center of each nickel wire, The intersection portion was bonded with an instantaneous adhesive (Aron Alpha (registered trademark), Toa Synthetic Co., Ltd.) to prepare an electrode. The electrode was evaluated, and the results are shown in Table 4.

The electrode had the thickest portion where the nickel wire overlapped, and the electrode had a thickness of 306 µm. The thickness of the catalyst layer was 6 µm. The porosity was 98.8%.

The mass per unit area of the electrode was 1.9 (mg / cm 2). The force (1) and (2) applied per unit mass and unit area were all below the lower limit of the measurement of a tensile tester. For this reason, the result of the 280 mm diameter coil winding evaluation (1) was less than 5%, and the part from which an electrode and a diaphragm peeled off increased. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 14 mm.

Moreover, when the ventilation resistance of the electrode was measured, it was 0.001 (kPa * s / m) or less in measurement condition 2. In measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring apparatus was measured as H (high), the ventilation resistance was 0.0005 (kPa · s / m).

Moreover, using the structure shown in FIG. 42, an electrode (cathode) was provided on the Ni mesh feeder, and electrolytic evaluation was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V.

Comparative Example 2-1

In Comparative Example 2-1, a thermocompression-bonding assembly in which an electrode was thermocompression-bonded to a diaphragm was produced with reference to the prior document (Example of Japanese Patent Laid-Open No. 58-48686).

Electrode coating was carried out in the same manner as in Example 2-1, using a nickel expanded metal having a gauge thickness of 100 µm and a porosity of 33% as the electrode base material for negative electrode electrolysis. Thereafter, one surface of the electrode was subjected to deactivation in the following order. A polyimide adhesive tape (Chuko Chemical Co., Ltd.) was adhered to one side of the electrode, and a PTFE dispersion (Mitsui DuPont Florochemical Co., Ltd., 31-JR (trade name)) was applied to the opposite side and dried for 10 minutes in a muffle furnace at 120 ° C. I was. The polyimide tape was peeled off and sintered for 10 minutes in a muffle furnace set at 380 ° C. This operation was repeated twice, and one surface of the electrode was inactivated.

A film formed of two layers of a perfluorocarbon polymer (C polymer) having a terminal functional group of "-COOCH ₃ " and a perfluorocarbon polymer (S polymer) having a terminal group of "-SO ₂ F" was produced. The C polymer layer was 3 mils thick and the S polymer layer was 4 mils thick. The saponification process was performed to this two-layer film, and the ion exchanger was introduce | transduced by hydrolysis to the terminal of a polymer. The C polymer end was hydrolyzed to the carboxylic acid group and the S polymer end to the sulfo group. The ion exchange capacity as the sulfonic acid group was 1.0 meq / g, and the ion exchange capacity as the carboxylic acid group was 0.9 meq / g.

On the surface having a carboxylic acid group as an ion exchanger, the inactivated electrode surface was faced to heat press to integrate the ion exchange membrane and the electrode. Even after thermocompression bonding, one side of the electrode was exposed, and no part of the electrode penetrated the membrane.

Then, in order to suppress adhesion of the bubble which generate | occur | produces during electrolysis to the film | membrane, the perfluorocarbon polymer mixture in which zirconium oxide and a sulfo group were introduce | transduced was apply | coated on both surfaces. Thus, the thermocompression bonding body of Comparative Example 2-1 was produced.

The force 1 applied per unit mass and unit area was measured using this thermocompression bonding body. As the electrode and the film were strongly bonded by thermocompression bonding, the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed so as not to move, and when the electrode was pulled upward with a stronger force, a part of the membrane was torn when a force of 1.50 (N / mg · cm 2) was applied. The force 1 applied per unit mass and unit area of the thermocompression bonding body of Comparative Example 2-1 was at least 1.50 (N / mg · cm 2), and was strongly bonded.

When the cylindrical winding winding evaluation (1) was performed, the contact area with the plastic pipe was less than 5%. On the other hand, when the column winding winding evaluation (2) of diameter 280 mm was performed, the electrode and the membrane were 100% bonded, but the diaphragm was not wound up to the cylinder initially. The result of the 145 mm diameter cylindrical winding evaluation (3) was also the same. This result meant that the handling of the film was impaired by the integrated electrodes, making it difficult to wind or bend the rolls. Handling property had a problem with "3". Membrane damage evaluation was "0". Moreover, when electrolytic evaluation was performed, the voltage was high, the current efficiency was low, the salt concentration (50% conversion value) in caustic soda became high, and electrolytic performance worsened.

In addition, the thickness of the electrode was 114 micrometers. The thickness of the catalyst layer was 14 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 13 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2.

Comparative Example 2-2

In Comparative Example 2-2, a nickel mesh having a wire diameter of 150 µm, 40 mesh, a gauge thickness of 300 µm, and a porosity of 58% was used as the electrode substrate for cathode electrolysis. Other than that, the thermocompression bonding body was produced similarly to the comparative example 2-1.

The force 1 applied per unit mass and unit area was measured using this thermocompression bonding body. As the electrode and the film were strongly bonded by thermocompression bonding, the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed so as not to move, and when the electrode was pulled upward with a stronger force, a part of the membrane was torn when a force of 1.60 (N / mg · cm 2) was applied. The force 1 applied per unit mass and unit area of the thermocompression bonding body of Comparative Example 2-2 was at least 1.60 (N / mg · cm 2), and was strongly bonded.

When the 280 mm diameter coil winding evaluation (1) was performed using this thermocompression bonding body, the contact area with the plastic pipe was less than 5%. On the other hand, when the column winding winding evaluation (2) of diameter 280 mm was performed, the electrode and the membrane were 100% bonded, but the diaphragm was not wound up to the cylinder initially. The result of the 145 mm diameter cylindrical winding evaluation (3) was also the same. This result meant that the handling of the film was impaired by the integrated electrodes, making it difficult to wind or bend the rolls. Handling property had a problem with "3". Moreover, when electrolytic evaluation was performed, the voltage was high, the current efficiency was low, the salt concentration in caustic soda became high, and electrolytic performance worsened.

In addition, the thickness of the electrode was 308 micrometers. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 23 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2.

TABLE 3

TABLE 4

In Table 4, before all the samples, the measurement of "force 1 per unit mass and unit area" and "force 2 per unit mass and unit area" was independent of the surface tension (i.e. flow Did not get off).

<Verification of the third embodiment>

As described below, an experimental example corresponding to the third embodiment (hereinafter simply referred to as "an example" in the section of <verification of the third embodiment>) and an experimental example not corresponding to the third embodiment (Simply referred to as "comparative example" in the following section in <Verification of Third Embodiment>) was prepared, and these were evaluated by the following method. The details will be described with reference to FIGS. 57 to 62 as appropriate.

(1) Electrolytic evaluation (voltage (V), current efficiency (%))

The electrolytic performance was evaluated by the following electrolytic experiment.

A positive electrode cell (anode terminal cell) made of titanium having a positive electrode chamber provided with a positive electrode and a negative electrode cell having a negative electrode chamber (cathode terminal cell) made of nickel provided with a negative electrode were opposed to each other. A pair of gaskets were arranged between the cells, and an ion exchange membrane was sandwiched between the pair of gaskets. The positive electrode cell, the gasket, the ion exchange membrane, the gasket, and the negative electrode were brought into close contact with each other to obtain an electrolytic cell.

As an anode, it produced by apply | coating, drying, and baking the mixed solution of ruthenium chloride, iridium chloride, and titanium tetrachloride on the titanium base material which carried out the blast and acid etching process as a pretreatment. The anode was fixed to the anode chamber by welding. As the negative electrode, those described in Examples and Comparative Examples were used. Nickel expanded metal was used as an electrical power collector of a negative electrode chamber. The size of the current collector was 95 mm in length × 110 mm in width. As the metal elastic body, a mattress woven from nickel thin wire was used. The mattress, which is a metal elastomer, was placed on the current collector. A nickel wire having a diameter of 150 µm was covered with a flat nickel mesh having a size of 40 mesh, and four corners of the Ni mesh were fixed to a current collector with a string made of Teflon (registered trademark). This Ni mesh was used as a feeder. In this electrolytic cell, the repulsive force of the mattress which is a metal elastic body was used so that it might become a zero gap structure. As the gasket, a rubber gasket made of EPDM (ethylene propylene diene) was used. As the diaphragm, the following ion exchange membrane was used.

As a reinforcing core material, it was made of polytetrafluoroethylene (PTFE) and 90 denier monofilament was used (hereinafter referred to as PTFE company). As the sacrificial yarn, a yarn in which 35 denier and 6 filament polyethylene terephthalate (PET) was added 200 twists / m was used. First, in each of the two directions of TD and MD, the woven fabric was plain so that two lines of PTFE yarn were disposed between 24 lines / inch and two sacrificed yarns were adjacent to adjacent PTFE yarns. The obtained woven fabric was crimped with a roll to obtain a woven fabric having a thickness of 70 µm.

Next, Resin A, CF ₂ = CF ₂ , a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ , having an ion exchange capacity of 0.85 mg equivalent / g. And Resin B of a dry resin having a copolymer of CF ₂ = CFOCF ₂ CF (CF ₂ ) OCF ₂ CF ₂ SO ₂ F and having an ion exchange capacity of 1.03 mg equivalent / g.

Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 µm and a resin B layer of 104 µm was obtained by a coextrusion T die method.

Subsequently, a hot plate having a heating source and a vacuum source therein and having fine holes on its surface was laminated in the order of release paper (conical embossing having a height of 50 μm), reinforcing material and film X, and hot plate. After heating and pressure-reducing for 2 minutes on the conditions of surface temperature 223 degreeC, and the pressure reduction degree 0.067 MPa, the composite film was obtained by removing a release paper.

The obtained composite membrane was saponified by immersing for 20 minutes in 80 degreeC aqueous solution containing 30 mass% of dimethyl sulfoxide (DMSO), and 15 mass% of potassium hydroxide (KOH). Then, it was immersed in 50 degreeC aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour, the counter ion of the ion exchange group was substituted by Na, and it washed with water continuously. Furthermore, it dried at 60 degreeC.

Further, a suspension obtained by adding 20% by mass of zirconium oxide having an average particle diameter (primary particle diameter) of 1 μm to a 5% by mass ethanol solution of the acid-type resin of the resin B was dispersed, and sprayed onto both surfaces of the composite membrane by a suspension spray method. And a coating of zirconium oxide were formed on the surface of the composite membrane to obtain an ion exchange membrane. The coating density of zirconium oxide was 0.5 mg / cm 2 as measured by fluorescence X-ray measurement. In addition, the average particle diameter was measured with the particle size distribution meter (for example, "SALD (trademark) 2200" by Shimadzu Corporation).

Salt electrolysis was performed using the said electrolysis cell. The brine concentration (sodium chloride concentration) of the anode chamber was adjusted to 205 g / L. The sodium hydroxide concentration of the cathode chamber was adjusted to 32 mass%. Each temperature of the anode chamber and the cathode chamber was adjusted such that the temperature in each electrolytic cell was 90 ° C. Salt electrolysis was performed at the current density of 6 kA / m <2>, and voltage and current efficiency were measured. Here, the current efficiency is a ratio of the amount of generated caustic soda to the current that flows, and the current efficiency decreases when impurity ions or hydroxide ions, not sodium ions, move the ion exchange membrane by the current that flows. The current efficiency was obtained by dividing the number of moles of caustic soda generated at a given time by the number of moles of electrons of the current flowing therein. The number of moles of caustic soda was determined by recovering the caustic soda produced by electrolysis into a poly tank and measuring the mass thereof.

(2) handling (response evaluation)

(A) The above-mentioned ion exchange membrane (diaphragm) was cut into the size of width 170mm, and the electrode obtained by the Example and comparative example which are mentioned later was cut into 95 * 110mm. The ion exchange membrane and the electrode were laminated and set on the Teflon plate. The distance between the positive electrode cell and the negative electrode cell used in the electrolytic evaluation was set to about 3 cm, the set laminate was lifted, and an operation of inserting and sandwiching the gap was performed. When this operation was performed, it was checked while operating whether the electrode was not twisted or dropped.

(B) The laminated body was set on the Teflon board similarly to said (A). The film | membrane part of a laminated body grasped the edge of two adjacent areas by hand, and it lifted so that a laminated body might become vertical. From this state, it moved so that the two edge | edges grasped | handed by hand might be made to become convex and concave. This operation was repeated once more to confirm the followability of the electrode to the film. The result was evaluated in four steps of 1-4 based on the following indicators.

1: Good handling

2: Handleable

3: difficult handling

4: almost impossible to handle

Here, with respect to the samples of Examples 3-4 and 3-6, as described later, the handling properties were evaluated even at the same size as the large electrolytic cell. The evaluation result of Example 3-4 and 3-6 was made into the index which evaluates the difference at the time of making evaluation of said (A), (B), and large size. That is, when the result of evaluating a small laminated body is "1" and "2", even if it was a large size, it evaluated that handling property became favorable.

(3) the ratio of the fixed area

The area (the sum of the part corresponding to the conducting surface and the part corresponding to the non conducting surface) of the surface facing the electrolytic electrode in the ion exchange membrane was calculated as the area S1. Next, the area of the electrode for electrolysis was computed as area S2 of an electricity supply surface. Areas S1 and S2 specified the area of the laminate of the ion exchange membrane and the electrode for electrolysis when viewed from the electrode side for electrolysis (see FIG. 57). In addition, since the shape of the electrode for electrolysis was less than 90% as a porosity even if it had a hole, the said electrode for electrolysis was regarded as a flat plate (the hole part also counts as area).

Also regarding the area S3 of the fixed area | region, it identified as area when the laminated body is top-viewed like FIG. 57 (area S3 'of the part corresponding only to an electrically conductive surface is also the same). In addition, when the PTFE tape mentioned later was fixed as a fixing member, the overlapping part of the tape shall not be counted as an area. In addition, when the PTFE yarn and the adhesive agent mentioned later were fixed as a fixing member, the area which exists in the back surface side of an electrode and a diaphragm was also included, and it counted as area.

As mentioned above, 100 * (S3 / S1) was computed as ratio ((%) of the area of the fixed area | region with respect to the area of the opposing surface with the electrode for electrolysis in an ion exchange membrane. Moreover, 100xS3 '/ S2 was computed as ratio (beta) of the area of the part corresponding only to the electrically conductive surface of the fixed area with respect to the area of the electrically conductive surface.

Example 3-1

As an electrode base material for negative electrode electrolysis, the electrolytic nickel foil whose gauge thickness is 22 micrometers was prepared. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. The arithmetic mean roughness Ra of the roughened surface was 0.96 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted.

A circular hole was drilled into this nickel foil by punching to obtain a porous foil. The porosity was 44%.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of the electrode produced in Example 3-1 was 24 µm. The thickness of the catalyst layer containing ruthenium oxide and cerium oxide was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side.

The electrode produced by the above method was cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode was disposed in a substantially central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm × 160 mm) balanced by 0.1N NaOH aqueous solution. Using a PTFE tape (manufactured by Nitto Denko), as shown in Fig. 57 (however, Fig. 57 is only an overview for explanation and the dimensions are not necessarily accurate. The same applies to the following drawings). Four sides were fixed to sandwich the electrodes. In Example 3-1, the PTFE tape was a fixing member, the ratio α was 60%, and the ratio β was 1.0%.

Even when the four corners of the membrane portion of the membrane-integrated electrode in which the membrane and the electrode were integrated were held, and the electrode was placed on the ground side and the membrane-integrated electrode was suspended to be parallel to the ground, the electrodes did not peel off or fall off. In addition, even when the both ends of one side were held and the membrane-integrated electrode was suspended so as to be perpendicular to the ground, the electrode did not peel off or fall off.

The membrane-integrated electrode was sandwiched between the anode cell and the cathode cell such that the surface on which the electrode was attached was the cathode chamber side. The cross-sectional structure forms a zero-gap structure from the cathode chamber side in the order of a current collector, a mattress, a nickel mesh feeder, an electrode, a film, and an anode.

Evaluation was performed about the obtained electrode. The results are shown in Table 5.

Low voltage, high current efficiency. Handling property was also relatively good as "2".

Example 3-2

As shown in FIG. 58, it evaluated similarly to Example 3-1 except having increased the area which a PTFE tape overlaps on an electrolytic surface. That is, in Example 3-2, since the area of the PTFE tape was increased in the in-plane direction of the electrode for electrolysis, the area of the electrolytic surface in the electrode for electrolysis was reduced than that in Example 3-1. In Example 3-2, the ratio α was 69% and the ratio β was 23%. Table 5 shows the results of the evaluation.

Low voltage, high current efficiency. Handling property was also good as "1".

Example 3-3

As shown in FIG. 59, it evaluated similarly to Example 3-1 except having increased the area which a PTFE tape overlaps on an electrolytic surface. That is, in Example 3-3, since the area of the PTFE tape was increased in the in-plane direction of the electrode for electrolysis, the area of the electrolytic surface in the electrode for electrolysis was reduced than that in Example 3-1. In Example 3-3, the ratio α was 87% and the ratio β was 67%. Table 5 shows the results of the evaluation.

Low voltage, high current efficiency. Handling property was also good as "1".

Example 3-4

The same electrode as in Example 3-1 was prepared and cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode was disposed in a substantially central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm x 160 mm) balanced by 0.1N NaOH aqueous solution. 60, the ion exchange membrane and the electrode were sewn so that the left side of an electrode might extend longitudinally as shown in FIG. From the edge of the electrode 10 mm in length and 10 mm in width, the PTFE yarn penetrates the thread from the back surface side of FIG. 60 toward the surface side, and the surface surface at 35 mm length and 10 mm width. It penetrates from the side to the back surface side, and penetrates the thread from the back surface side to the surface side again at a part of 60 mm length and 10 mm horizontally, and penetrates from the surface surface side to the back side surface at a length of 85 mm length and 10 mm width. I was. In the part where the yarn penetrates the ion exchange membrane, a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₂ ) OCF ₂ CF ₂ SO ₂ F with an ion exchange capacity of 1.03 mg equivalent / g The solution which disperse | distributed resin S to 5 mass% in ethanol was apply | coated.

As described above, in Example 3-4, the ratio α was 0.35% and the ratio β was 0.86%.

Even if the four corners of the membrane portion of the membrane-integrated electrode in which the membrane and the electrode were integrated were held, the electrode was placed on the ground side, and the membrane-integrated electrode was suspended so as to be parallel to the ground. Holding both ends of one side and suspending the membrane-integrated electrode perpendicular to the ground did not cause the electrode to fall.

Evaluation was performed about the obtained electrode. The results are shown in Table 5.

Low voltage, high current efficiency. Handling property was also relatively good as "2".

Moreover, in Example 3-4, the ion exchange membrane and the electrode which changed into large size were prepared. Four ion exchange membranes of 1.5 m in length and 2.5 m in width and 0.3 m in length and 2.4 m in width were prepared. A negative electrode was arranged on the carboxylic acid layer side of the ion exchange membrane without a gap, and the negative electrode and the ion exchange membrane were bonded by PTFE company, and the laminated body was produced. In this example, the ratio α was 0.013% and the ratio β was 0.017%.

The operation of attaching the membrane-integrated electrode in which the membrane and the electrode were integrated into the large electrolytic cell was performed, but it was able to be attached smoothly.

Example 3-5

The same electrode as in Example 3-1 was prepared and cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode was disposed in a substantially central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm × 160 mm) balanced by 0.1N NaOH aqueous solution. The ion exchange membrane and the electrode were fixed using the polypropylene fixing resin shown in FIG. In other words, at one part 20 mm in length and 20 mm in width from the edge of the electrode, one more part in 20 mm length and 20 mm in width from the corner located at the lower side, and two more in total. Installed. The same solution as in Example 3-4 was applied to the portion where the fixing resin penetrated the ion exchange membrane.

As mentioned above, in Example 3-5, fixing resin and resin S became a fixing member, ratio (alpha) was 0.47% and ratio (beta) was 1.1%.

Even if the four corners of the membrane portion of the membrane-integrated electrode in which the membrane and the electrode were integrated were held, the electrode was placed on the ground side, and the membrane-integrated electrode was suspended so as to be parallel to the ground. Holding both ends of one side and suspending the membrane-integrated electrode perpendicular to the ground did not cause the electrode to fall.

Evaluation was performed about the obtained electrode. The results are shown in Table 5.

Low voltage, high current efficiency. Handling property was also relatively good as "2".

Example 3-6

The same electrode as in Example 3-1 was prepared and cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode was disposed in a substantially central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm × 160 mm) balanced by 0.1N NaOH aqueous solution. As shown in FIG. 62, the ion exchange membrane and the electrode were fixed using the cyanoacrylate type adhesive (brand name: Aaron Alpha, Toa Synthetic Co., Ltd.). That is, five places (all equal intervals) on one side of the electrode and eight places (all equal intervals) were fixed on one side of the electrode with an adhesive.

As described above, in Example 3-6, the adhesive became a fixing member, the ratio α was 0.78%, and the ratio β was 1.9%.

Even if the four corners of the membrane portion of the membrane-integrated electrode in which the membrane and the electrode were integrated were held, the electrode was placed on the ground side, and the membrane-integrated electrode was suspended so as to be parallel to the ground. Holding both ends of one side and suspending the membrane-integrated electrode perpendicular to the ground did not cause the electrode to fall.

Evaluation was performed about the obtained electrode. The results are shown in Table 5.

Low voltage, high current efficiency. Handling property was also relatively good as "1".

Moreover, in Example 3-6, the ion exchange membrane and the electrode which changed into large size were prepared. Four ion exchange membranes of 1.5 m in length and 2.5 m in width and 0.3 m in length and 2.4 m in width were prepared. The four negative electrodes connected the edge part of one side of a horizontal with the said adhesive agent, and made one large negative electrode (1.2 m in length, 2.4 m in width). This large cathode was adhered to the carboxylic acid layer side center portion of the ion exchange membrane by Aaron Alpha to prepare a laminate. That is, similarly to Fig. 62, five places (all equal intervals) on one side of the electrode and eight places (all equal intervals) were fixed on one side of the electrode by the adhesive. In this example, the ratio α was 0.019% and the ratio β was 0.024%.

The operation of attaching the membrane-integrated electrode in which the membrane and the electrode were integrated into the large electrolytic cell was performed, but it was able to be attached smoothly.

Example 3-7

The same electrode as in Example 3-1 was prepared and cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode was disposed in a substantially central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm × 160 mm) balanced by 0.1N NaOH aqueous solution. The same solution as in Example 3-4 was applied to fix the ion exchange membrane and the electrode. In other words, at one part 20 mm in length and 20 mm in width from the edge of the electrode, one more part in 20 mm length and 20 mm in width from the corner located at the lower side, and two more in total. Installed (see FIG. 61).

As described above, in Example 3-7, Resin S became a fixing member, the ratio α was 2.0%, and the ratio β was 4.8%.

Even if the four corners of the membrane portion of the membrane-integrated electrode in which the membrane and the electrode were integrated were held, the electrode was placed on the ground side, and the membrane-integrated electrode was suspended so as to be parallel to the ground. Holding both ends of one side and suspending the membrane-integrated electrode perpendicular to the ground did not cause the electrode to fall.

Evaluation was performed about the obtained electrode. The results are shown in Table 5.

Low voltage, high current efficiency. Handling property was also relatively good as "2".

Comparative Example 3-1

Evaluation was performed similarly to Example 3-1 except having increased the area which a PTFE tape overlaps on an electrolytic surface. That is, in Comparative Example 3-1, since the area of the PTFE tape was increased in the in-plane direction of the electrode for electrolysis, the area of the electrolytic surface in the electrode for electrolysis was reduced than in Example 3-1. In Comparative Example 3-1, the ratio α was 93% and the ratio β was 83%. Table 5 shows the results of the evaluation.

The voltage was high and the current efficiency was low. Handling property was good as "1".

Comparative Example 3-2

Evaluation was performed similarly to Example 3-1 except having increased the area which a PTFE tape overlaps on an electrolytic surface. Table 5 shows the results of the evaluation. That is, in Comparative Example 3-2, the area of the PTFE tape was increased in the in-plane direction of the electrode for electrolysis.

In Comparative Example 3-2, the ratio α and the ratio β were 100%, and because the entire electrolytic surface was a fixed region covered with PTFE, the electrolyte could not be supplied and could not be electrolyzed. Handling property was good as "1".

Comparative Example 3-3

Evaluation was performed similarly to Example 3-1 except having not used PTFE tape, ie, the ratio (alpha) and the ratio (beta) were 0%. Table 5 shows the results of the evaluation.

Low voltage, high current efficiency. On the other hand, since there were no fixed regions of the diaphragm and the electrode, the diaphragm and the electrode could not be handled as a laminate (integrated body), and the handling property was "4".

The evaluation results of Examples 3-1 to 7 and Comparative Examples 3-1 to 3 are shown in Table 5 below.

TABLE 5

<Verification of the fourth embodiment>

As described below, an experimental example corresponding to the fourth embodiment (hereinafter simply referred to as "an example" in the section of <verification of the fourth embodiment>) and an experimental example not corresponding to the fourth embodiment (Hereinafter, simply referred to as "comparative example" in the section on <Verification of Fourth Embodiment>) were prepared, and these were evaluated by the following method. The detail is demonstrated, referring FIGS. 79-90 suitably.

〔Assessment Methods〕

(1) Opening rate

The electrode was cut out to a size of 130 mm x 100 mm. The average value which measured ten points of surface uniformly was computed using the dejimatic thickness gauge (Mitsutoyo Corporation make, minimum indication 0.001mm). The volume was computed using this as thickness of an electrode (gauge thickness). Then, the mass was measured by the electronic balance, and the porosity or the porosity was computed from the specific gravity of metal (specific gravity of nickel = 8.908 g / cm <3>, specific gravity of titanium = 4.506 g / cm <3>).

Porosity (porosity) (%) = (1- (electrode mass) / (electrode volume × specific gravity of metal)) × 100

(2) mass per unit area (mg / cm 2)

The electrode was cut out to a size of 130 mm x 100 mm, and the mass was measured by electronic balance. The mass per unit area was computed by dividing the value by area (130 mm x 100 mm).

(3) Force applied per unit mass and unit area (1) (adhesive force) (N / mg · cm 2)

[Method (i)]

A tensile compression tester was used for the measurement (Imada Co., Ltd., tester main body: SDT-52NA type tensile compression tester, weighting meter: SL-6001 type weighting machine).

The blast process was performed with the alumina of particle number 320 on the nickel plate of thickness 1.2mm and width-and-length 200mm. The arithmetic mean surface roughness Ra of the nickel plate after blasting was 0.7 micrometers. Here, the stylus type surface roughness measuring instrument SJ-310 (Mitsutoyo Co., Ltd.) was used for surface roughness measurement. The measurement sample was installed on the surface plate parallel to the ground, and the arithmetic mean roughness Ra was measured under the following measurement conditions. The measurement described the average value at the time of six implementations.

<Shape of the needle> Cone taper angle = 60 °, tip radius = 2 μm, static measuring force = 0.75 mN

<Roughness standard> JIS2001

<Evaluation curve> R

<Filter> GAUSS

<Cut-off value λc> 0.8 mm

<Cut off value λs> 2.5 μm

<Number of Sections> 5

<Jeonju, Huju> Yes

The nickel plate was fixed to the lower chuck of the tensile compression tester so as to be vertical.

As the diaphragm, the following ion exchange membrane A was used.

As a reinforcing core material, it was made of polytetrafluoroethylene (PTFE) and 90 denier monofilament was used (hereinafter referred to as PTFE company). As the sacrificial yarn, a yarn in which twisted polyethylene denephthalate (PET) of 35 deniers and 6 filaments was applied 200 times / m was used (hereinafter referred to as PET yarn). First, in each of the two directions of TD and MD, the woven fabric was plain so that two lines of PTFE yarn were disposed between 24 lines / inch and two sacrificed yarns were adjacent to adjacent PTFE yarns. The obtained woven fabric was crimped with a roll to obtain a woven fabric having a thickness of 70 µm.

Next, Resin A, CF ₂ = CF ₂ , a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ , having an ion exchange capacity of 0.85 mg equivalent / g. And Resin B of a dry resin having a copolymer of CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and having an ion exchange capacity of 1.03 mg equivalent / g.

Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 µm and a resin B layer of 104 µm was obtained by a coextrusion T die method.

Subsequently, a hot plate having a heating source and a vacuum source therein and having fine holes on its surface was laminated in the order of release paper (conical embossing having a height of 50 μm), reinforcing material and film X, and hot plate. After heating and pressure-reducing for 2 minutes on the conditions of surface temperature 223 degreeC, and the pressure reduction degree 0.067 MPa, the composite film was obtained by removing a release paper.

The obtained composite membrane was saponified by immersing for 20 minutes in 80 degreeC aqueous solution containing 30 mass% of dimethyl sulfoxide (DMSO), and 15 mass% of potassium hydroxide (KOH). Then, it was immersed in 50 degreeC aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour, the counter ion of the ion exchange group was substituted by Na, and it washed with water continuously. Furthermore, it dried at 60 degreeC.

Further, a suspension obtained by adding 20 mass% of zirconium oxide having a primary particle size of 1 μm to a 5 mass% ethanol solution of the acid-type resin of the resin B was dispersed, sprayed onto both surfaces of the composite membrane by a suspension spray method, and A coating was formed on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconium oxide was 0.5 mg / cm 2 as measured by fluorescence X-ray measurement. In addition, the average particle diameter was measured by the particle size distribution meter ("SALD (trademark) 2200" by Shimadzu Corporation).

The ion exchange membrane (diaphragm) obtained above was immersed in pure water for 12 hours or more, and used for the test. The nickel plate was sufficiently wetted with pure water and brought into contact with water under tension. At this time, it installed so that the position of the upper surface of a nickel plate and an ion exchange membrane may match.

The electrolytic electrode sample (electrode) used for the measurement was cut | disconnected to 130 mm long. Ion exchange membrane A was cut out to 170 mm in length and width. One side of the electrode was sandwiched between two stainless plates (1 mm in thickness, 9 mm in length, and 170 mm in width), and the stainless plate and the center of the electrode were aligned so as to be aligned, and then fixed evenly with four clips. The center of the stainless plate was fitted to the chuck above the tensile compression tester, and the electrodes were suspended. At this time, the load applied to the tester was 0N. First, the stainless plate, the electrode, and the clip assembly were removed from the tensile compression tester, and soaked in a batt containing pure water in order to sufficiently wet the electrode with pure water. After that, the center of the stainless steel plate was placed on the upper chuck of the tensile compression tester and the electrode was suspended.

The upper chuck of the tensile compression tester was lowered, and the electrolytic electrode sample was adhered to the surface of the ion exchange membrane by pure surface tension. The adhesive surface at this time was 130 mm in width and 110 mm in length. Pure water in the bottle was sprayed on the entire electrode and the ion exchange membrane, so that the diaphragm and the electrode were sufficiently wet again. Then, the roller which wound the EPDM sponge rubber of the independent foaming type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) was pressed lightly from the top of the electrode, and it rolled downwards from the top to remove the extra pure water. The roller was rolled only once.

Weight measurement was started by raising the electrode at a rate of 10 mm / min, and the weight when the overlapping portion of the electrode and the diaphragm became 130 mm in width and 100 mm in length was recorded. This measurement was performed three times and the average value was calculated.

This average value was divided by the area of the overlapped portion of the electrode and the ion exchange membrane and the electrode mass of the portion overlapped with the ion exchange membrane to calculate the force (1) applied per unit mass and unit area. The electrode mass of the part which overlapped with the ion exchange membrane was calculated | required by the proportional calculation from the value obtained from the mass per unit area (mg / cm <2>) of said (2).

The environment of the measurement room was 23 ± 2 ° C. and 30 ± 5% relative humidity.

In addition, when the electrode used by the Example and the comparative example was adhere | attached on the ion-exchange membrane adhered by the surface tension to the nickel plate fixed vertically, it adhered by self-supporting, without flowing down or peeling.

In addition, the schematic diagram of the evaluation method of the applied force 1 was shown in FIG.

In addition, the minimum of the measurement of the tensile tester was 0.01 (N).

(4) Force applied per unit mass and unit area (2) (adhesive force) (N / mg · cm 2)

[Method (ii)]

A tensile compression tester was used for the measurement (Imada Co., Ltd., tester main body: SDT-52NA type tensile compression tester, weighting meter: SL-6001 type weighting machine).

The same nickel plate as the method (i) was fixed to the lower chuck of the tensile compression tester so as to be vertical.

The electrolytic electrode sample (electrode) used for the measurement was cut | disconnected to 130 mm long. Ion exchange membrane A was cut out to 170 mm in length and width. One side of the electrode was sandwiched between two stainless plates (1 mm in thickness, 9 mm in length, and 170 mm in width), and the stainless plate and the center of the electrode were aligned so as to be aligned, and then fixed evenly with four clips. The center of the stainless plate was fitted to the chuck above the tensile compression tester, and the electrodes were suspended. At this time, the load applied to the tester was 0N. First, from the tensile compression tester, the stainless plate, the electrode, and the clip assembly were removed, and soaked in a batt containing pure water in order to sufficiently wet the electrode with pure water. Then, the center of the stainless plate was pinched again on the chuck | zipper of a tension compression tester, and the electrode was suspended.

The upper chuck of the tensile compression tester was lowered, and the electrolytic electrode sample was adhered to the nickel plate surface by the surface tension of the solution. The adhesive surface at this time was 130 mm in width and 110 mm in length. The pure water in the bottle was sprayed on the electrode and the whole of the nickel plate, and the nickel plate and the electrode were made sufficiently wet again. Then, the roller which wound the EPDM sponge rubber of the independent foaming type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) was pressed lightly from the top of the electrode, and was rolled from the top to the bottom, and the excess solution was removed. The roller was rolled only once.

Weight measurement was started by raising the electrode at a rate of 10 mm / min, and the weight when the overlapping portion in the longitudinal direction of the electrode and the nickel plate became 100 mm was recorded. This measurement was performed three times and the average value was calculated.

The average value was divided by the area of the overlapped portion of the electrode and the nickel plate and the electrode mass of the portion overlapped with the nickel plate to calculate the force 2 applied per unit mass and unit area. The electrode mass of the part which overlapped with the diaphragm was calculated | required by the proportional calculation from the value obtained from the mass per unit area (mg / cm <2>) of said (2).

In addition, the environment of the measurement chamber was 23 ± 2 ° C. and 30 ± 5% relative humidity.

In addition, when the electrode used by the Example and the comparative example was adhere | attached by the surface tension to the nickel plate fixed vertically, it adhered by self-supporting, without flowing down or peeling.

In addition, the minimum of the measurement of the tensile tester was 0.01 (N).

(5) 280 mm diameter cylindrical winding evaluation method (1) (%)

(Membrane and cylinder)

Evaluation method (1) was implemented in the following procedures.

The ion exchange membrane A (diaphragm) created in [Method (i)] was cut into a size of 170 mm in width and length. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. In Examples 33 and 34, since the electrode was integrated into the ion exchange membrane by heat press, an integrated body of the ion exchange membrane and the electrode was prepared (the electrode was 130 mm long). After the ion exchange membrane was sufficiently immersed in pure water, it was placed on the curved surface of a pipe made of plastic (polyethylene) having an outer diameter of 280 mm. Then, the excess solution was removed with the roller which wound the EPDM sponge rubber of the independent foaming type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm). The roller rolled the ion exchange membrane image toward the left side from the left side of the schematic diagram shown in FIG. The roller was rolled only once. After 1 minute, the ratio of the part where the ion exchange membrane and the pipe electrode made of plastic with an outer diameter of 280 mm were in close contact was measured.

(6) 280 mm diameter cylindrical winding evaluation method (2) (%)

(Membrane and electrode)

Evaluation method (2) was implemented in the following procedures.

The ion exchange membrane A (diaphragm) created in [Method (i)] was cut to a size of 170 mm in width and length, and the electrode was cut to 130 mm in width and length. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminated body was placed on the curved surface of the plastic (polyethylene) pipe of outer diameter 280 mm so that an electrode might become outer side. Subsequently, while pressing the roller which wound EPDM sponge rubber of the independent foam type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) lightly from the top of an electrode, it rolls toward the right side from the left side of the schematic diagram shown in FIG. Removed. The roller was rolled only once. After 1 minute, the ratio of the part where the ion exchange membrane and the electrode were in close contact was measured.

(7) 145 mm diameter cylindrical winding evaluation method (3) (%)

(Membrane and electrode)

The evaluation method (3) was implemented in the following procedures.

The ion exchange membrane A (diaphragm) created in [Method (i)] was cut to a size of 170 mm in width and length, and the electrode was cut to 130 mm in width and length. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. The laminate was placed on the curved surface of a pipe made of plastic (polyethylene) having an outer diameter of 145 mm so that the electrode was outside. Subsequently, while pressing the roller which wound EPDM sponge rubber of independent foam type of thickness 5mm in the vinyl chloride pipe (outer diameter 38mm) lightly from the top of an electrode, it rolls toward the right side from the left side of the schematic diagram shown in FIG. Removed. The roller was rolled only once. After 1 minute, the ratio of the part where the ion exchange membrane and the electrode were in close contact was measured.

(8) handling (response evaluation)

(A) The ion-exchange membrane A (diaphragm) created by [method (i)] was cut into the size of 170 mm horizontally and 95 x 110 mm. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. In each Example, the ion exchange membrane and the electrode were fully immersed in three kinds of solutions of sodium bicarbonate aqueous solution, 0.1N NaOH aqueous solution, and pure water, and were laminated and set on a Teflon plate. The distance between the positive electrode cell and the negative electrode cell used in the electrolytic evaluation was set to about 3 cm, the set laminate was lifted, and an operation of inserting and sandwiching the gap was performed. When this operation was performed, it was checked while operating whether the electrode was not twisted or dropped.

(B) The ion exchange membrane A (diaphragm) created in [Method (i)] was cut to a size of 170 mm in width and length, and the electrode was cut to 95 × 110 mm. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. In each Example, the ion exchange membrane and the electrode were fully immersed in three kinds of solutions of sodium bicarbonate aqueous solution, 0.1N NaOH aqueous solution, and pure water, and were laminated and set on a Teflon plate. The two adjacent corners of the membrane part of the laminated body were grasped by hand, and the laminated body was lifted up so that it was vertical. From this state, it moved so that the two edge | edges grasped | handed by hand might be made to become convex and concave. This was repeated once more to confirm the followability of the electrode to the film. The result was evaluated in four steps of 1-4 based on the following indicators.

1: Good handling

2: Handleable

3: difficult handling

4: almost impossible to handle

Here, with respect to the sample of Example 4-28, the electrode was handled at the same size as the large electrolytic cell of 1.3 m x 2.5 m and the ion exchange membrane with the size of 1.5 m x 2.8 m. The evaluation result ("3" as described later) of Example 28 was made into the index which evaluates the difference in the evaluation of said (A), (B), and when it was set as large size. That is, when the result of evaluating a small laminated body is "1" and "2", even if it was a large size, it evaluated that there was no problem in handling property.

(9) Electrolytic evaluation (voltage (V), current efficiency (%), salt concentration in caustic soda (ppm, 50% equivalent))

The electrolytic performance was evaluated by the following electrolytic experiment.

A positive electrode cell (anode terminal cell) made of titanium having a positive electrode chamber provided with a positive electrode and a negative electrode cell having a negative electrode chamber (cathode terminal cell) made of nickel provided with a negative electrode were opposed to each other. A pair of gaskets were arrange | positioned between cells, and the laminated body (the laminated body of an ion exchange membrane A and an electrode for electrolysis) was sandwiched between a pair of gaskets. Here, both of the ion exchange membrane A and the electrode for electrolysis were sandwiched directly between the gaskets. Then, an anode cell, a gasket, a laminate, a gasket, and a cathode were brought into close contact to obtain an electrolysis cell, and an electrolytic cell containing the same was prepared.

As an anode, it produced by apply | coating, drying, and baking the mixed solution of ruthenium chloride, iridium chloride, and titanium tetrachloride on the titanium base material which carried out the blast and acid etching process as a pretreatment. The anode was fixed to the anode chamber by welding. As the negative electrode, those described in Examples and Comparative Examples were used. Nickel expanded metal was used as an electrical power collector of a negative electrode chamber. The size of the current collector was 95 mm in length × 110 mm in width. As the metal elastic body, a mattress woven from nickel thin wire was used. The mattress, which is a metal elastomer, was placed on the current collector. A nickel wire having a diameter of 150 µm was covered with a flat nickel mesh having a size of 40 mesh, and four corners of the Ni mesh were fixed to a current collector with a string made of Teflon (registered trademark). This Ni mesh was used as a feeder. In this electrolytic cell, the repulsive force of the mattress which is a metal elastic body is used, and it has a zero gap structure. As the gasket, a rubber gasket made of EPDM (ethylene propylene diene) was used. As a diaphragm, the ion exchange membrane A (160 mm long) created by [method (i)] was used.

Salt electrolysis was performed using the said electrolysis cell. The brine concentration (sodium chloride concentration) of the anode chamber was adjusted to 205 g / L. The sodium hydroxide concentration of the cathode chamber was adjusted to 32 mass%. Each temperature of the anode chamber and the cathode chamber was adjusted such that the temperature in each electrolytic cell was 90 ° C. Salt electrolysis was performed at a current density of 6 kA / m 2, and the salt concentration in voltage, current efficiency, and caustic soda was measured. Here, the current efficiency is a ratio of the amount of generated caustic soda to the current that flows, and the current efficiency decreases when impurity ions or hydroxide ions, not sodium ions, move the ion exchange membrane by the current that flows. The current efficiency was obtained by dividing the number of moles of caustic soda generated at a given time by the number of moles of electrons of the current flowing therein. The number of moles of caustic soda was determined by recovering the caustic soda produced by electrolysis into a poly tank and measuring the mass thereof. The sodium chloride concentration in caustic soda represented the value converted from caustic soda to 50%.

Table 6 also shows the specifications of the electrode and the power feeder used in Examples and Comparative Examples.

(11) Measurement of the thickness of the catalyst layer, the electrode base for electrolysis, the thickness of the electrode

The thickness of the electrode base material for electrolysis computed the average value which measured 10 points uniformly in-plane using the dejimatic thickness gauge (Mitsutoyo Corporation make, minimum display 0.001mm). This was made into the thickness (gauge thickness) of the electrode base material for electrolysis. The thickness of the electrode computed the average value which measured 10 points uniformly in-plane with the dejimatic thickness gauge similarly to the electrode base material. This was made into the thickness (gauge thickness) of an electrode. The thickness of the catalyst layer was obtained by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

(12) elastic deformation test of electrode

The ion-exchange membrane A (diaphragm) and the electrode which were created by [method (i)] were cut | judged to the size of 110 mm width and height. The ion exchange membrane was used for the test after immersion in pure water for 12 hours or more. After the laminate was fabricated by overlapping the ion exchange membrane and the electrode under the condition of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, as shown in FIG. 83, no gap was formed in the pipe made of PVC having an outer diameter of φ32 mm and a length of 20 cm. Wound up. The wound laminate was fixed using a binding band made of polyethylene so as not to be peeled or relaxed from the PVC pipe. It kept in this state for 6 hours. Then, the binding band was removed and the laminated body was loosened from the pipe made from PVC. Only the electrode was placed on the surface plate, and the heights L ₁ and L ₂ of the portion floating from the surface plate were measured to obtain an average value. This value was used as an index of electrode deformation. That is, the smaller the value is, the harder it is to deform.

In addition, when using an expanded metal, when winding up, there are two types, SW direction and LW direction. In this test, it wound up to SW direction.

Moreover, about the softness after plastic deformation was evaluated about the electrode which a deformation | transformation (electrode which did not return to the original flat state) by the method as shown in FIG. That is, the electrode which had a deformation | transformation was placed on the diaphragm fully immersed in pure water, the one end was fixed, the opposing edge part which floated was pressed to the diaphragm, the force was opened, and it evaluated whether the electrode which a deformation | transformation followed the diaphragm.

(13) membrane damage evaluation

As the diaphragm, the following ion exchange membrane B was used.

As the reinforcing core material, polytetrafluoroethylene (PTFE), which was made into a yarn shape by applying a twist of 900 times / m to a 100 denier tape yarn (hereinafter referred to as PTFE company). As a sacrificial warp yarn, a yarn in which 35 denier and 8 filament polyethylene terephthalate (PET) was twisted 200 times / m was used (hereinafter referred to as PET yarn). As a weft sacrificial yarn, a yarn in which 35 denier and 8 filament polyethylene terephthalate (PET) was twisted 200 times / m was used. First, a PTFE woven fabric was plain weave so that two lines of 24 lines / inch and a sacrificial yarn were disposed between adjacent PTFE yarns to obtain a woven fabric having a thickness of 100 µm.

Next, CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ is a copolymer of dry resin with an ion exchange capacity of 0.92 mg equivalent / g (CF), CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F is a copolymer of a dry resin (B1) having an ion exchange capacity of 1.10 mg equivalent / g. Using these polymers (A1) and (B1), the two-layer film X having the thickness of the polymer (A1) layer of 25 µm and the polymer (B1) layer of 89 µm was obtained by the coextrusion T die method. In addition, the ion exchange capacity of each polymer showed the ion exchange capacity when the ion exchanger precursor of each polymer was hydrolyzed and converted into the ion exchanger.

In addition, separately prepared polymer (B2) of a dry resin having a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and having an ion exchange capacity of 1.10 mg equivalent / g. This polymer was single-layer extruded and the film Y of 20 micrometers was obtained.

Subsequently, on a hot plate having a heating source and a vacuum source therein and having micropores on the surface thereof, they were laminated in the order of the release paper, the film Y, the reinforcing material and the film X, and the hot plate temperature was 225 ° C. and the pressure reduction degree was 0.022 MPa. After heating and pressure-reducing for 2 minutes on conditions, the composite film was obtained by removing a release paper. The obtained composite membrane was saponified by immersion in an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) for 1 hour, and then immersed in 0.5 N NaOH for 1 hour to replace ions attached to the ion exchanger with Na. Continually washed. Furthermore, it dried at 60 degreeC.

In addition, hydrolyzed polymer (B3) of a dry resin having a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F, having an ion exchange capacity of 1.05 mg equivalent / g. After that, it was in acid form by hydrochloric acid. Zirconium oxide particles having an average particle diameter of 0.02 µm were prepared in a solution obtained by dissolving the polymer (B3 ') in the acid form in a 50/50 (mass ratio) mixture of water and ethanol at a ratio of 5% by mass. B3 ') and the mass ratio of zirconium oxide particle | grains were added so that it might be 20/80. Thereafter, the mixture was dispersed in a suspension of zirconium oxide particles in a ball mill to obtain a suspension.

This suspension was applied to both surfaces of the ion exchange membrane by the spray method and dried to obtain an ion exchange membrane B having a coating layer containing a polymer (B3 ') and zirconium oxide particles. It was 0.35 mg / cm <2> when the coating density of zirconium oxide was measured by the fluorescent X-ray measurement.

The positive electrode used the same thing as (9) electrolytic evaluation.

As the negative electrode, those described in Examples and Comparative Examples were used. The current collector, the mattress, and the electric power feeder of the negative electrode chamber used the same thing as (9) Electrolytic evaluation. In other words, the Ni mesh is used as the feeder, and the repulsive force of the mattress, which is a metal elastic body, is used to form a zero gap structure. The gasket also used the same thing as (9) electrolytic evaluation. An ion exchange membrane B prepared by the above method was used as the diaphragm. That is, the electrolytic cell similar to (9) was prepared except the sandwiching body of the ion exchange membrane B and the electrode for electrolysis was sandwiched between a pair of gaskets.

Salt electrolysis was performed using the said electrolysis cell. The brine concentration (sodium chloride concentration) of the anode chamber was adjusted to 205 g / L. The sodium hydroxide concentration of the cathode chamber was adjusted to 32 mass%. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell was 70 ° C. Salt electrolysis was performed at a current density of 8 kA / m 2. Electrolysis was stopped 12 hours after the start of the electrolysis, and the ion exchange membrane B was taken out and the damage state was observed.

"○" means that there is no damage. "X" means that there is damage on almost the entire surface of the ion exchange membrane.

(14) air resistance of the electrode

The air permeation resistance of the electrode was measured using the air permeability tester KES-F8 (trade name, Kato Tech Co., Ltd.). The unit of ventilation resistance value is kPa * s / m. The measurement was performed 5 times and the average value is shown in Table 7. The measurement was performed under the following two conditions. In addition, the temperature of the measurement chamber was 24 degreeC and the relative humidity was 32%.

ㆍ Measurement condition 1 (ventilation resistance 1)

Piston Speed: 0.2 cm / s

Aeration amount: 0.4 cc / ㎠ / s

Measuring range: SENSE L (low)

Sample size: 50 mm x 50 mm

ㆍ Measurement condition 2 (ventilation resistance 2)

Piston Speed: 2 cm / s

Aeration amount: 4 cc / ㎠ / s

Measuring range: SENSE M (medium) or H (high)

Sample size: 50 mm x 50 mm

Example 4-1

As an electrode base material for negative electrode electrolysis, the electrolytic nickel foil whose gauge thickness is 16 micrometers was prepared. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. Arithmetic mean roughness Ra of the roughened surface was 0.71 micrometer. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted.

A circular hole was drilled into this nickel foil by punching to obtain a porous foil. Opening rate was 49%.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of the electrode produced in Example 4-1 was 24 µm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side. In addition, it is the total thickness of ruthenium oxide and cerium oxide.

Table 7 shows the measurement results of the adhesive force of the electrode produced by the above method. Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2.

The electrode produced by the above method was cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The roughened surface of the electrode is made to face the position near the center of the carboxylic acid layer side of the ion exchange membrane A (size is 160 mm x 160 mm) produced by 0.1N NaOH aqueous solution equilibrated, It adhered by the surface tension of aqueous solution.

Even when the four corners of the membrane portion of the membrane-integrated electrode in which the membrane and the electrode were integrated were held, and the electrode was placed on the ground side and the membrane-integrated electrode was suspended to be parallel to the ground, the electrodes did not peel off or fall off. In addition, even when the both ends of one side were held and the membrane-integrated electrode was suspended so as to be perpendicular to the ground, the electrode did not peel off or fall off.

The membrane-integrated electrode was sandwiched between the anode cell and the cathode cell such that the surface on which the electrode was attached was the cathode chamber side. The cross-sectional structure forms a zero-gap structure from the cathode chamber side in the order of a current collector, a mattress, a nickel mesh feeder, an electrode, a film, and an anode.

Electrolytic evaluation was performed about the obtained electrode. The results are shown in Table 7.

It showed low voltage, high current efficiency and low caustic concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF (fluorescence X-ray analysis), the roughened surface remained almost 100% of the coating, and the non-roughened surface reduced the coating. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 4-2

In Example 4-2, an electrolytic nickel foil having a gauge thickness of 22 µm was used as the electrode substrate for negative electrode electrolysis. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. The arithmetic mean roughness Ra of the roughened surface was 0.96 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. The porosity was 44%. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 29 μm. The thickness of the catalyst layer was 7 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode. The coating was also formed on the unroughened side.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0033 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF, the roughened surface remained almost 100% of the coating, and the non-roughened surface reduced the coating. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 4-3

In Example 4-3, an electrolytic nickel foil having a gauge thickness of 30 µm was used as the electrode substrate for negative electrode electrolysis. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. The arithmetic mean roughness Ra of the roughened surface was 1.38 m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. The porosity was 44%. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 38 μm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF, the roughened surface remained almost 100% of the coating, and the non-roughened surface reduced the coating. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 4-4

In Example 4-4, electrolytic nickel foil having a gauge thickness of 16 µm was used as the electrode substrate for negative electrode electrolysis. One surface of this nickel foil was roughened by electrolytic nickel plating. Arithmetic mean roughness Ra of the roughened surface was 0.71 micrometer. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. The porosity was 75%. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 24 μm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after electrolysis was measured by XRF, the roughened surface remained almost 100% of the coating, and the non-roughened surface reduced the coating. This indicates that the surface opposite to the membrane (roughened surface) contributes to the electrolysis, and the opposite surface not facing the membrane exhibits good electrolytic performance even if there is little or no coating.

Example 4-5

Example 4-5 prepared the electrolytic nickel foil whose gauge thickness is 20 micrometers as an electrode base material for negative electrode electrolysis. Both surfaces of this nickel foil were roughened by electrolytic nickel plating. The arithmetic mean roughness Ra of the roughened surface was 0.96 mu m. Both sides had the same roughness. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Opening rate was 49%. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 30 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0023 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

In addition, when the coating amount after the electrolysis was measured by XRF, almost 100% of the coating remained on both sides. When compared with Examples 4-1 to 4-4, the opposite side not facing the film indicates that good electrolytic performance can be exhibited even if there is little or no coating.

Example 4-6

Example 4-6 evaluated similarly to Example 4-1 except having performed coating to the electrode base material for negative electrode electrolysis by ion plating, and the result was shown in Table 7. In addition, ion plating formed into a film at the film-forming pressure of 7x10 <^-2> Pa in argon / oxygen atmosphere using the heating temperature of 200 degreeC and Ru metal target. The coating formed was ruthenium oxide.

The thickness of the electrode was 26 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-7

Example 4-7 produced the electrode base material for negative electrode electrolysis by the electroforming method. The shape of the photomask was made into the shape which arranged the square of 0.485 mm x 0.485 mm lengthwise and horizontally at 0.15 mm space | interval. By performing exposure, image development, and electroplating in order, the nickel porous foil with a gauge thickness of 20 micrometers and a porosity of 56% was obtained. Arithmetic mean roughness Ra of the surface was 0.71 m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 37 μm. The thickness of the catalyst layer was 17 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-8

Example 4-8 was created by the electroforming method as an electrode base material for cathode electrolysis, and the gauge thickness was 50 µm and the porosity was 56%. Arithmetic mean roughness Ra of the surface was 0.73 m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 60 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0032 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-9

In Example 4-9, a nickel nonwoven fabric (manufactured by Nico Techno Co., Ltd.) having a gauge thickness of 150 µm and a porosity of 76% was used as the electrode substrate for cathode electrolysis. Nickel fiber diameter of the nonwoven fabric was about 40 micrometers, and basis weight was 300 g / m <2>. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 165 mu m. The thickness of the catalyst layer was 15 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 29 mm, and did not return to the original flat state. Ta

Therefore, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastic deformation was carried out, it was confirmed that the diaphragm could be contacted with a small force, and this electrode was found to have good handling property.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0612 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was good as "0".

Example 4-10

In Example 4-10, a nickel nonwoven fabric (manufactured by Nico Techno Co., Ltd.) having a gauge thickness of 200 µm and a porosity of 72% was used as the electrode substrate for cathode electrolysis. The nickel fiber diameter of the nonwoven fabric was about 40 micrometers, and basis weight was 500 g / m <2>. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 215 탆. The thickness of the catalyst layer was 15 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

Bar subjected to transformation test of the electrodes, the average value of L _1, L ₂ is 40 mm, it did not go back up to the original flat state. Therefore, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastic deformation was carried out, it was confirmed that the diaphragm could be contacted with a small force, and this electrode was found to have good handling property.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0164 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was good as "0".

Example 4-11

In Example 4-11, foamed nickel (manufactured by Mitsubishi Material Co., Ltd.) having a gauge thickness of 200 µm and a porosity of 72% was used as the electrode substrate for cathode electrolysis. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

In addition, the thickness of the electrode was 210 micrometers. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 17 mm and it did not return to the original flat state. Therefore, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastic deformation was carried out, it was confirmed that the diaphragm could be contacted with a small force, and this electrode was found to have good handling property.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0402 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was good as "0".

Example 4-12

In Example 4-12, a nickel mesh having a wire diameter of 50 µm, 200 mesh, a gauge thickness of 100 µm, and a porosity of 37% was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. Even if blasting was performed, the porosity did not change. Since it is difficult to measure the roughness of the wire mesh surface, in Example 4-12, at the time of blasting, the nickel plate of thickness 1mm was blasted simultaneously, and the surface roughness of the nickel plate was made into the surface roughness of the wire mesh. The arithmetic mean roughness Ra of one wire mesh was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 110 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0.5 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0154 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-13

In Example 4-13, a nickel mesh having a wire diameter of 65 µm, 150 mesh, a gauge thickness of 130 µm, and a porosity of 38% was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. Even if blasting was performed, the porosity did not change. Since it is difficult to measure the roughness of the wire mesh surface, in Example 4-13, the nickel plate of thickness 1mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was made into the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.66 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, the said evaluation was performed like Example 4-1, and the result was shown in Table 7.

The thickness of the electrode was 133 mu m. The thickness of the catalyst layer was 3 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 6.5 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0124 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was "2", and it was judged that handling was possible as a large laminated body. The film damage evaluation was also good at "0".

Example 4-14

In Example 4-14, the same substrate (gauge thickness 30 µm, porosity 44%) as in Example 4-3 was used as the electrode substrate for cathode electrolysis. The electrolytic evaluation was performed with the structure similar to Example 4-1 except having not provided the nickel mesh electric power feeder. That is, the cross-sectional structure of the cell forms a zero-gap structure from the cathode chamber side in the order of the current collector, the mattress, the film integrated electrode, and the anode, and the mattress functions as a power feeder. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-15

In Example 4-15, the same substrate (gauge thickness 30 µm, porosity 44%) as in Example 4-3 was used as the electrode substrate for cathode electrolysis. In place of the nickel mesh feeder, a negative electrode having a deteriorated and high electrolytic voltage used in Reference Example 1 was provided. Other than that, electrolytic evaluation was performed by the same structure as Example 4-1. That is, the cross-sectional structure of the cell forms a zero-gap structure from the cathode chamber side in the order of the current collector, the mattress, and the negative electrode (functioning as a power feeder), the cathode, the diaphragm, and the anode, which are deteriorated and the electrolytic voltage is increased. The cathode whose deterioration has increased the electrolytic voltage functions as a feeder. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-16

As an electrode base material for positive electrode electrolysis, titanium foil whose gauge thickness is 20 micrometers was prepared. The roughening process was given to both surfaces of the titanium foil. The titanium foil was punched out, and a circular hole was drilled into a porous foil. The diameter of the hole was 1 mm and the porosity was 14%. Arithmetic mean roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. Ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L, iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) with a iridium concentration of 100 g / L, titanium tetrachloride (Wakkoyaku Industry Co., Ltd.), ruthenium element and iridium It mixed so that the molar ratio of an element and a titanium element might be 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred to prepare a positive electrode coating solution.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). After apply | coating the said coating liquid to titanium porous foil, it dried for 10 minutes at 60 degreeC, and baked for 10 minutes at 475 degreeC. After repeating these series of application | coating, drying, plasticity, and baking a series of operations, it baked at 520 degreeC for 1 hour.

The electrode produced by the above method was cut out to a size of 95 mm in length and 110 mm in width for electrolytic evaluation. The ion exchange membrane A (size: 160 mm x 160 mm) prepared in [Method (i)] equilibrated with 0.1 N NaOH aqueous solution was brought into close contact with the surface tension of the aqueous solution at a position near the center of the sulfonic acid layer side.

The negative electrode was prepared in the following order. First, a nickel wire mesh of 150 µm in diameter and 40 mesh was prepared as a substrate. After performing blasting with alumina as pretreatment, it was immersed in 6N hydrochloric acid for 5 minutes, and it fully wash | cleaned and dried with pure water. Next, a ruthenium chloride solution (Tanaka Precious Metal Industry Co., Ltd.) and cerium chloride (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Then, drying for 10 minutes at 50 degreeC, plasticity for 3 minutes at 300 degreeC, and baking for 10 minutes at 550 degreeC was performed. Then, baking was performed at 550 degreeC for 1 hour. A series of operations of these coating, drying, plasticity, and baking were repeated.

Nickel expanded metal was used as an electrical power collector of a negative electrode chamber. The size of the current collector was 95 mm in length × 110 mm in width. As the metal elastic body, a mattress woven from nickel thin wire was used. The mattress, which is a metal elastomer, was placed on the current collector. The negative electrode created by the above method was covered thereon, and four corners of the mesh were fixed to the current collector with a string made of Teflon (registered trademark).

Even if the four edges of the membrane portion of the membrane-integrated electrode in which the membrane and the anode were integrated were held, and the electrode was brought to the ground side and the membrane-integrated electrode was suspended so as to be parallel to the ground, the electrodes did not peel off or twisted. In addition, even when the both ends of one side were held and the membrane-integrated electrode was suspended so as to be perpendicular to the ground, the electrode did not peel off or fall off.

The positive electrode, which had been used in Reference Example 3, had a deteriorated and high electrolytic voltage fixed by welding, and the membrane-integrated electrode was sandwiched between the positive electrode cell and the negative electrode so that the surface on which the electrode was attached was on the positive electrode side. That is, the cross-sectional structure of the cell was formed from the cathode chamber side in order from the current collector, the mattress, the cathode, the diaphragm, the titanium porous foil anode, and the anode deteriorated to increase the electrolytic voltage to form a zero gap structure. The anode which deteriorated and the electrolytic voltage increased was functioning as a power feeder. In addition, between the titanium porous foil anode and the anode which deteriorated and the electrolytic voltage became high, it was only physically contacting and was not fixed by welding.

With this structure, evaluation was performed similarly to Example 4-1, and the result was shown in Table 7.

The thickness of the electrode was 26 μm. The thickness of the catalyst layer was 6 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 4 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0060 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-17

In Example 4-17, titanium foil having a gauge thickness of 20 μm and a porosity of 30% was used as the electrode substrate for positive electrode electrolysis. Arithmetic mean roughness Ra of the surface was 0.37 μm. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-16, and showed the result in Table 7.

The thickness of the electrode was 30 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 5 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0030 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

[Example 4-18]

In Example 4-18, titanium foil having a gauge thickness of 20 μm and a porosity of 42% was used as the electrode substrate for positive electrode electrolysis. Arithmetic mean roughness Ra of the surface was 0.38 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-16, and showed the result in Table 7.

The thickness of the electrode was 32 mu m. The thickness of the catalyst layer was 12 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 2.5 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0022 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-19

In Example 4-19, titanium foil having a gauge thickness of 50 µm and a porosity of 47% was used as the electrode substrate for positive electrode electrolysis. Arithmetic mean roughness Ra of the surface was 0.40 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-16, and showed the result in Table 7.

The thickness of the electrode was 69 μm. The thickness of the catalyst layer was 19 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation test of the electrode was conducted, the average value of L ₁ and L ₂ was 8 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0024 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-20

In Example 4-20, a titanium nonwoven fabric having a gauge thickness of 100 µm, a titanium fiber diameter of about 20 µm, a basis weight of 100 g / m 2, and a porosity of 78% was used as the electrode substrate for anode electrolysis. Other than that, it evaluated similarly to Example 4-16, and showed the result in Table 7.

The thickness of the electrode was 114 탆. The thickness of the catalyst layer was 14 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 2 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0228 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-21

In Example 4-21, a titanium wire mesh having a gauge thickness of 120 µm, a titanium fiber diameter of about 60 µm, and a 150 mesh was used as the electrode substrate for anode electrolysis. The porosity was 42%. The blasting was performed with the alumina of particle number 320. Since it is difficult to measure the roughness of the wire mesh surface, in Example 4-21, the titanium plate of thickness 1mm was blasted simultaneously at the time of blasting, and the surface roughness of the titanium plate was made into the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.60 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-16, and showed the result in Table 7.

The thickness of the electrode was 140 μm. The thickness of the catalyst layer was 20 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

Sufficient adhesion was observed.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 10 mm. It was found that the elastic deformation region was a wide electrode.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0132 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". The film damage evaluation was also good at "0".

Example 4-22

In Example 4-22, a positive electrode was used in the same manner as in Example 4-16 as the positive electrode feeder, and the same nonwoven fabric as in Example 4-20 was used as the positive electrode. In the same manner as in Example 4-15, a cathode deteriorated to increase the electrolytic voltage was used as the cathode feeder, and the same nickel foil electrode as in Example 4-3 was used as the cathode. The cross-sectional structure of the cell is arranged in the order of the current collector, the mattress, the deteriorated high voltage cathode, the nickel porous foil cathode, the diaphragm, the titanium nonwoven anode, and the deteriorated positive electrode voltage from the cathode chamber side to form a zero gap structure. The negative electrode and the positive electrode which are deteriorated and the electrolytic voltage increased are functioning as a power feeder. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode (anode) was 114 μm, and the thickness of the catalyst layer was 14 μm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode (anode). The thickness of the electrode (cathode) was 38 μm, and the thickness of the catalyst layer was 8 μm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode (cathode).

Sufficient adhesion was observed for both the positive and negative electrodes.

When the deformation test of the electrode (anode) was performed, the average value of L ₁ and L ₂ was 2 mm. When the deformation test of the electrode (cathode) was conducted, the average value of L ₁ and L ₂ was 0 mm.

The ventilation resistance of the electrode (anode) was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0228 (kPa · s / m) under measurement condition 2. The ventilation resistance of the electrode (cathode) was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

It also showed low voltage, high current efficiency, low caustic salt concentration. Handling property was also good as "1". Film damage evaluation of both the positive electrode and the negative electrode was also good as "0". In Example 4-22, the negative electrode was stuck on one side of the diaphragm and the positive electrode was stuck on the opposite side, and the film damage evaluation was performed by combining the negative electrode and the positive electrode.

Example 4-23

In Example 4-23, a microporous membrane "Zirfon Perl UTP 500" manufactured by Agfa Corporation was used.

Zirfon membrane was used for the test after immersion in pure water for more than 12 hours. Otherwise, the above evaluation was performed in the same manner as in Example 4-3, and the results are shown in Table 7.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 0 mm. It was found that the elastic deformation region was a wide electrode.

As in the case where the ion exchange membrane was used as the diaphragm, sufficient adhesive force was observed, the microporous membrane and the electrode were in close contact with each other by the surface tension, and the handling property was "1".

Reference Example 1

In Reference Example 1, a cathode used in a large electrolytic cell for eight years as a cathode and deteriorated to increase the electrolytic voltage was used. The negative electrode was placed on the mattress of the negative electrode chamber in place of the nickel mesh feeder, and the electrolytic evaluation was performed by sandwiching the ion exchange membrane A prepared in [Method (i)]. In Reference Example 1, the membrane-integrated electrode was not used, and the cross-sectional structure of the cell was formed from the cathode chamber side by arranging a current collector, a mattress, and a cathode, an ion exchange membrane A, and an anode deteriorated to increase the electrolytic voltage to form a zero gap structure. I was.

As a result of the electrolytic evaluation by this structure, the voltage was 3.04V, the current efficiency was 97.0%, and the salt concentration (50% conversion value) in caustic soda was 20 ppm. Since the cathode deteriorated, the result was a high voltage.

Reference Example 2

In Reference Example 2, a nickel mesh feeder was used as the cathode. That is, electrolysis was performed by the nickel mesh which was not catalyst coated.

A nickel mesh negative electrode was provided on the mattress of the negative electrode chamber, and the electrolytic evaluation was performed through the ion exchange membrane A created in [method (i)]. The cross-sectional structure of the electric cell of Reference Example 2 was arranged in the order of the current collector, the mattress, the nickel mesh, the ion exchange membrane A, and the anode from the cathode chamber side to form a zero gap structure.

As a result of electrolytic evaluation by this structure, the voltage was 3.38V, the current efficiency was 97.7%, and the salt concentration (50% conversion value) in caustic soda was 24 ppm. Since the negative catalyst was not coated, the result was a high voltage.

Reference Example 3

In Reference Example 3, a positive electrode used in a large electrolytic cell for about 8 years as a positive electrode and having a deteriorated electrolytic voltage was used.

The cross-sectional structure of the electrolytic cell of Reference Example 3 is arranged from the cathode chamber side in the order of the current collector, the mattress, the cathode, and the ion exchange membrane A prepared in [Method (i)], and the anode deteriorated to increase the electrolytic voltage. Formed.

As a result of the electrolytic evaluation by this structure, the voltage was 3.18V, the current efficiency was 97.0%, and the salt concentration (50% conversion value) in caustic soda was 22 ppm. Since the anode deteriorated, the result was a high voltage.

Example 4-24

In Example 4-24, a nickel expanded metal having a gauge thickness of 100 µm and a porosity of 33% after pull roll processing was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 4-24, a nickel plate having a thickness of 1 mm was simultaneously blasted at the time of blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.68 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 114 탆. The thickness of the catalyst layer was 14 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 67.5 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.05 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) was 64%, and the result of the 145 mm cylindrical coil winding evaluation (3) was 22%, and the part from which an electrode and a diaphragm peeled was increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 13 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2.

Example 4-25

In Example 4-25, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 16% after pull roll processing was used as the electrode substrate for negative electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 4-25, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was made the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 107 탆. The thickness of the catalyst layer was 7 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

The mass per unit area was 78.1 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.04 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) was 37%, and the result of the 145 mm cylindrical coil winding evaluation (3) was 25%, and the part from which an electrode and a diaphragm peeled off increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 18.5 mm. When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0176 (kPa · s / m) under measurement condition 2.

Example 4-26

In Example 4-26, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 40% after pull roll processing was used as the electrode substrate for negative electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 4-26, a nickel plate having a thickness of 1 mm was simultaneously blasted at the time of blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.70 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Coating on the electrode base for electrolysis was performed by the same ion plating as Example 4-6. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 110 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The force 1 applied per unit mass and unit area was a small value of 0.07 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is 80%, and the result of the 145 mm cylindrical coil winding evaluation (3) is 32%, and the part from which an electrode and a diaphragm peeled off increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 11 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0030 (kPa · s / m) under measurement condition 2.

Example 4-27

In Example 4-27, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 58% after pull roll processing was used as an electrode base material for cathode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 4-27, a nickel plate having a thickness of 1 mm was simultaneously blasted at the time of blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 109 탆. The thickness of the catalyst layer was 9 µm by subtracting the thickness of the electrode base material for electrolysis from the thickness of the electrode.

The force 1 applied per unit mass and unit area was a small value of 0.06 (N / mg · cm 2). For this reason, the result of the cylindrical winding evaluation 2 of 280 mm diameter was 69%, and the result of the cylindrical winding evaluation 3 of 145 mm diameter was 39%, and the part from which an electrode and a diaphragm peeled off increased. This tends to cause the electrode to peel off when handling the film-integrated electrode, and there is a problem such that the electrode peels off from the film and falls during handling. Handling property also had a problem with "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 11.5 mm.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0028 (kPa · s / m) under measurement condition 2.

Example 4-28

In Example 4-28, a nickel wire mesh having a gauge thickness of 300 µm and a porosity of 56% was used as the electrode substrate for negative electrode electrolysis. Since it is difficult to measure the surface roughness of the wire mesh, in Example 4-28, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Arithmetic mean roughness Ra was 0.64 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-1, and showed the result in Table 7.

The thickness of the electrode was 308 mu m. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 49.2 (mg / cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation 2 was 88%, and the result of the 145 mm cylindrical coil winding evaluation 3 was 42%, and the part from which an electrode and a diaphragm peeled off increased. This is easy when the electrode is peeled off when handling the film-integrated electrode, and the electrode peels off from the film and falls during handling. There is a problem in handling property as "3". It actually operated in large size and evaluated as "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 23 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2.

Example 4-29

In Example 4-29, a nickel wire mesh having a gauge thickness of 200 µm and a porosity of 37% was used as the electrode substrate for cathode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the wire mesh, in Example 4-29, a nickel plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.65 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, adhesiveness was performed similarly to Example 4-1 as a result of electrode electrolysis evaluation and the measurement of adhesive force. The results are shown in Table 7.

The thickness of the electrode was 210 μm. The thickness of the catalyst layer was 10 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 56.4 mg / cm 2. For this reason, the adhesiveness of an electrode and a diaphragm was bad in 63% of the result of the 145 mm diameter coil winding evaluation method (3). This is easy when the electrode is peeled off when handling the film-integrated electrode, and the electrode peels off from the film and falls during handling. There is a problem in handling property as "3". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 19 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0096 (kPa · s / m) under measurement condition 2.

Example 4-30

In Example 4-30, a titanium expanded metal having a gauge thickness of 500 μm and a porosity of 17% after full roll processing was used as the electrode substrate for positive electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 4-30, a titanium plate having a thickness of 1 mm was simultaneously blasted at the time of blasting, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.60 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, it evaluated similarly to Example 4-16, and showed the result in Table 7.

In addition, the thickness of the electrode was 508 micrometers. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 152.5 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.01 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is less than 5%, and the result of the 145 mm cylindrical coil winding evaluation (3) is less than 5%, and the part from which an electrode and a diaphragm peeled off increased. When handling the membrane-integrated electrode, the electrode was likely to be peeled off, and during the handling, the electrode was peeled off from the film and fell. Handling property also had a problem with "4". Membrane damage evaluation was "0".

Bar subjected to transformation test of the electrode, the electrode is not to be recalled while dried in the form of a PVC pipe, it could not measure the value of L _1, L _2.

The ventilation resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0072 (kPa · s / m) under measurement condition 2.

Example 4-31

In Example 4-31, a titanium expanded metal having a gauge thickness of 800 m and a porosity of 8% after pull roll processing was used as the electrode substrate for positive electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 4-31, a titanium plate having a thickness of 1 mm was blasted simultaneously at the time of blasting, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.61 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, the said evaluation was performed like Example 4-16, and the result was shown in Table 7.

The thickness of the electrode was 808 μm. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 251.3 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.01 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is less than 5%, and the result of the 145 mm cylindrical coil winding evaluation (3) is less than 5%, and the part from which an electrode and a diaphragm peeled off increased. When handling the membrane-integrated electrode, the electrode was likely to be peeled off, and during the handling, the electrode was peeled off from the film and fell. Handling property also had a problem with "4". Membrane damage evaluation was "0".

Bar subjected to transformation test of the electrode, the electrode is not to be recalled while dried in the form of a PVC pipe, it could not measure the value of L _1, L _2.

The ventilation resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1, and 0.0172 (kPa · s / m) under measurement condition 2.

Example 4-32

In Example 4-32, titanium expanded metal having a gauge thickness of 1000 µm and a porosity of 46% after pull roll processing was used as the electrode substrate for positive electrode electrolysis. The blasting was performed with the alumina of particle number 320. The porosity did not change even after blasting. Since it is difficult to measure the surface roughness of the expanded metal, in Example 4-32, a titanium plate having a thickness of 1 mm was simultaneously blasted at the time of blasting, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. Arithmetic mean roughness Ra was 0.59 mu m. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted. Other than that, the said evaluation was performed like Example 4-16, and the result was shown in Table 7.

In addition, the thickness of the electrode was 1011 micrometers. The thickness of the catalyst layer was 11 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

The mass per unit area was 245.5 (mg / cm 2). The force 1 applied per unit mass and unit area was a small value of 0.01 (N / mg · cm 2). For this reason, the result of the 280 mm diameter coil winding evaluation (2) is less than 5%, and the result of the 145 mm cylindrical coil winding evaluation (3) is less than 5%, and the part from which an electrode and a diaphragm peeled off increased. When handling the membrane-integrated electrode, the electrode was likely to be peeled off, and during the handling, the electrode was peeled off from the film and fell. Handling property also had a problem with "4". Membrane damage evaluation was "0".

Bar subjected to transformation test of the electrode, the electrode is not to be recalled while dried in the form of a PVC pipe, it could not measure the value of L _1, L _2.

The airflow resistance of the electrode was measured to be 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0027 (kPa · s / m) under measurement condition 2.

Example 4-33

In Example 4-33, the membrane electrode assembly in which the electrode was thermocompression-bonded to the diaphragm was produced with reference to the prior document (Example of Japanese Patent Laid-Open No. 58-48686).

Electrode coating was performed in the same manner as in Example 4-1, using a nickel expanded metal having a gauge thickness of 100 µm and a porosity of 33% as the electrode base material for the cathode electrolysis. Thereafter, one surface of the electrode was subjected to deactivation in the following order. A polyimide adhesive tape (Chuko Chemical Co., Ltd.) was adhered to one side of the electrode, and a PTFE dispersion (Mitsui DuPont Florochemical Co., Ltd., 31-JR (trade name)) was applied to the opposite side and dried for 10 minutes in a muffle furnace at 120 ° C. I was. The polyimide tape was peeled off and sintered for 10 minutes in a muffle furnace set at 380 ° C. This operation was repeated twice, and one surface of the electrode was inactivated.

A film formed of two layers of a perfluorocarbon polymer (C polymer) having a terminal functional group of "-COOCH ₃ " and a perfluorocarbon polymer (S polymer) having a terminal group of "-SO ₂ F" was produced. The C polymer layer was 3 mils thick and the S polymer layer was 4 mils thick. The saponification process was performed to this two-layer film, and the ion exchanger was introduce | transduced by hydrolysis to the terminal of a polymer. The C polymer end was hydrolyzed to the carboxylic acid group and the S polymer end to the sulfo group. The ion exchange capacity as the sulfonic acid group was 1.0 meq / g, and the ion exchange capacity as the carboxylic acid group was 0.9 meq / g.

On the surface having a carboxylic acid group as an ion exchanger, the inactivated electrode surface was faced to heat press to integrate the ion exchange membrane and the electrode. Even after thermocompression bonding, one side of the electrode was exposed, and no part of the electrode penetrated the membrane.

Then, in order to suppress adhesion of the bubble which generate | occur | produces during electrolysis to the film | membrane, the perfluorocarbon polymer mixture in which zirconium oxide and a sulfo group were introduce | transduced was apply | coated on both surfaces. Thus, the membrane electrode assembly of Example 4-33 was produced.

Using the membrane electrode assembly, the force 1 applied per unit mass and unit area was measured. As a result, the electrode and the membrane were strongly joined by thermocompression bonding, and therefore the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed so as not to move, and when the electrode was pulled upward with a stronger force, a part of the membrane was torn when a force of 1.50 (N / mg · cm 2) was applied. The force 1 applied per unit mass and unit area of the membrane electrode assembly of Example 4-33 was at least 1.50 (N / mg · cm 2), and was strongly bonded.

When the cylindrical winding winding evaluation (1) was performed, the contact area with the plastic pipe was less than 5%. On the other hand, when the column winding winding evaluation (2) of diameter 280 mm was performed, the electrode and the membrane were 100% bonded, but the diaphragm was not wound up to the cylinder initially. The result of the 145 mm diameter cylindrical winding evaluation (3) was also the same. This result meant that the handling of the film was impaired by the integrated electrodes, making it difficult to wind or bend the rolls. Handling property had a problem with "3". Membrane damage evaluation was "0". Moreover, when electrolytic evaluation was performed, the voltage was high, the current efficiency was low, the salt concentration (50% conversion value) in caustic soda became high, and electrolytic performance worsened.

In addition, the thickness of the electrode was 114 micrometers. The thickness of the catalyst layer was 14 micrometers by subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 13 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0168 (kPa · s / m) under measurement condition 2.

Example 4-34

In Example 4-34, a nickel mesh having a line diameter of 150 µm, 40 mesh, a gauge thickness of 300 µm, and a porosity of 58% was used as the electrode substrate for cathode electrolysis. Other than that, the membrane electrode assembly was produced similarly to Example 4-33.

Using the membrane electrode assembly, the force 1 applied per unit mass and unit area was measured. As a result, the electrode and the membrane were strongly joined by thermocompression bonding, and therefore the electrode did not move upward. Therefore, the ion exchange membrane and the nickel plate were fixed so as not to move, and when the electrode was pulled upward with a stronger force, a part of the membrane was torn when a force of 1.60 (N / mg · cm 2) was applied. The force 1 applied per unit mass and unit area of the membrane electrode assembly of Example 4-34 was at least 1.60 (N / mg · cm 2), and was strongly bonded.

The 280 mm-diameter cylindrical winding evaluation (1) was performed using this membrane electrode assembly, and the contact area with the plastic pipe was less than 5%. On the other hand, when the column winding winding evaluation (2) of diameter 280 mm was performed, the electrode and the membrane were 100% bonded, but the diaphragm was not wound up to the cylinder initially. The result of the 145 mm diameter cylindrical winding evaluation (3) was also the same. This result meant that the handling of the film was impaired by the integrated electrodes, making it difficult to wind or bend the rolls. Handling property had a problem with "3". Moreover, when electrolytic evaluation was performed, the voltage was high, the current efficiency was low, the salt concentration in caustic soda became high, and electrolytic performance worsened.

In addition, the thickness of the electrode was 308 micrometers. The thickness of the catalyst layer was 8 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 23 mm.

When the air resistance of the electrode was measured, it was 0.07 (kPa · s / m) or less under measurement condition 1 and 0.0034 (kPa · s / m) under measurement condition 2.

Example 4-35

As an electrode base material for cathode electrolysis, a nickel wire having a gauge thickness of 150 µm was prepared. The roughening process by this nickel wire was performed. Since it is difficult to measure the surface roughness of a nickel wire, in Example 4-35, the nickel plate of thickness 1mm was blasted simultaneously at the time of blasting, and the surface roughness of the nickel plate was made into the surface roughness of the nickel wire. The blasting was performed with the alumina of particle number 320. Arithmetic mean roughness Ra was 0.64 mu m.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. An application roll wound with rubber (Inoac Corporation, E-4088 (trade name), thickness 10 mm) made of foamed EPDM (ethylene propylene diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride); It was installed so that the coating liquid always contacted. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of one nickel wire produced in Example 4-35 was 158 micrometers.

The nickel wire produced by the above method was cut to lengths of 110 mm and 95 mm. As shown in Fig. 85, the 110 mm nickel wire and the 95 mm nickel wire were vertically overlapped at the center of each nickel wire, and the intersection portion was bonded with Aaron Alpha to prepare an electrode. The electrode was evaluated, and the results are shown in Table 7.

The electrode had the thickest portion where the nickel wire overlapped, and the electrode had a thickness of 306 µm. The thickness of the catalyst layer was 6 µm. The porosity was 99.7%.

The mass per unit area of the electrode was 0.5 (mg / cm 2). The force (1) and (2) applied per unit mass and unit area were all below the lower limit of the measurement of a tensile tester. For this reason, the result of the 280 mm diameter coil winding evaluation (1) was less than 5%, and the part from which an electrode and a diaphragm peeled off increased. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 15 mm.

The ventilation resistance of the electrode was measured and found to be 0.001 (kPa · s / m) or less under measurement condition 2. In measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring apparatus was measured as H (high), the ventilation resistance value was 0.0002 (kPa · s / m).

Moreover, using the structure shown in FIG. 86, an electrode (cathode) was provided on the Ni mesh feeder, and electrolysis evaluation was performed by the method described in (9) Electrolysis evaluation. As a result, the voltage was as high as 3.16 V.

Example 4-36

In Example 4-36, using the electrode produced in Example 4-35, as shown in FIG. 87, the 110 mm nickel wire and the 95 mm nickel wire were vertically overlapped at the center of each nickel wire, The intersection portion was bonded with Aaron Alpha to prepare an electrode. The electrode was evaluated, and the results are shown in Table 7.

The electrode had the thickest portion where the nickel wire overlapped, and the electrode had a thickness of 306 µm. The thickness of the catalyst layer was 6 µm. The porosity was 99.4%.

The mass per unit area of the electrode was 0.9 (mg / cm 2). The force (1) and (2) applied per unit mass and unit area were all below the lower limit of the measurement of a tensile tester. For this reason, the result of the 280 mm diameter coil winding evaluation (1) was less than 5%, and the part from which an electrode and a diaphragm peeled off increased. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 16 mm.

The ventilation resistance of the electrode was measured and found to be 0.001 (kPa · s / m) or less under measurement condition 2. In measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring apparatus was measured as H (high), the ventilation resistance was 0.0004 (kPa · s / m).

Moreover, using the structure shown in FIG. 88, an electrode (cathode) was provided on the Ni mesh feeder, and electrolytic evaluation was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V.

Example 4-37

In Example 4-37, using the electrode produced in Example 4-35, as shown in FIG. 89, the 110 mm nickel wire and the 95 mm nickel wire were vertically overlapped at the center of each nickel wire, The intersection portion was bonded with Aaron Alpha to prepare an electrode. The electrode was evaluated, and the results are shown in Table 7.

The electrode had the thickest portion where the nickel wire overlapped, and the electrode had a thickness of 306 µm. The thickness of the catalyst layer was 6 µm. The porosity was 98.8%.

The mass per unit area of the electrode was 1.9 (mg / cm 2). The force (1) and (2) applied per unit mass and unit area were all below the lower limit of the measurement of a tensile tester. For this reason, the result of the 280 mm diameter coil winding evaluation (1) was less than 5%, and the part from which an electrode and a diaphragm peeled off increased. Handling property also had a problem with "4". Membrane damage evaluation was "0".

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 14 mm.

Moreover, when the ventilation resistance of the electrode was measured, it was 0.001 (kPa * s / m) or less in measurement condition 2. In measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring apparatus was measured as H (high), the ventilation resistance was 0.0005 (kPa · s / m).

Moreover, using the structure shown in FIG. 90 for an electrode, the electrode (cathode) was provided on the Ni mesh feed material, and electrolytic evaluation was performed by the method as described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V.

Comparative Example 4-1

(Preparation of Catalyst)

0.728 g of silver nitrate (Wako Pure Chemical Industries, Ltd.) and 1.86 g of cerium nitrate hexahydrate (Wako Pure Chemical Industries, Ltd.) were added to 150 ml of pure water to prepare an aqueous metal salt solution. 240 g of pure water was added to 100 g of an aqueous 15% tetramethylammonium hydroxide solution (Wako Pure Chemical Industries, Ltd.) to prepare an alkaline solution. While stirring the alkaline solution using a magnetic stirrer, the aqueous metal salt solution was added dropwise at 5 ml / min using a burette. The suspension containing the produced metal hydroxide fine particles was suction filtered, and then washed with water to remove alkali. Thereafter, the filtrate was transferred into 200 ml of 2-propanol (Kishida Chemical Co., Ltd.) and redispersed for 10 minutes with an ultrasonic disperser (US-600T, Nippon Seiki Co., Ltd.) to obtain a uniform suspension.

0.36 g of hydrophobic carbon black (Denka black (trademark) AB-7 (brand name), Denki Kagaku Kogyo Co., Ltd.), 0.84 g of hydrophilic carbon black (Ketjen black (trademark) EC-600JD (brand name), Mitsubishi Chemical Corporation) It was dispersed in 100 ml of 2-propanol and dispersed for 10 minutes by an ultrasonic disperser to obtain a suspension of carbon black. The suspension of the metal hydroxide precursor and the suspension of carbon black were mixed and dispersed for 10 minutes by an ultrasonic disperser. The suspension was suction filtered and dried at room temperature for half a day to obtain carbon black obtained by dispersing and fixing a metal hydroxide precursor. Subsequently, using an inert gas firing furnace (VMF165 type, Yamada Electric Co., Ltd.), firing was carried out at 400 ° C. for 1 hour in a nitrogen atmosphere to obtain carbon black A in which the electrode catalyst was dispersed and fixed.

(Powder making for reaction layer)

To 1.6 g of carbon black A in which the electrode catalyst was dispersed and immobilized, 0.84 ml of surfactant Triton (registered trademark) X-100 (trade name, ICN Biomedical) diluted with 20% by weight of pure water, and 15 ml of pure water were added to an ultrasonic disperser. Disperse for 10 minutes. 0.664 g of PTFE (polytetrafluoroethylene) dispersion (PTFE30J (trade name), Mitsui DuPont Florochemical Co., Ltd.) was added to this dispersion, followed by stirring for 5 minutes, followed by suction filtration. Furthermore, it dried at 80 degreeC in 1 hour for 1 hour, grind | pulverized with the mill, and obtained the powder A for reaction tanks.

(Production of Powder for Gas Diffusion Layer)

20 g of hydrophobic carbon black (Denka Black (registered trademark) AB-7 (trade name)), 50 ml of surfactant Triton (registered trademark) X-100 (trade name) diluted to 20% by weight in pure water, ultrasonic wave 360 ml Dispersion was performed for 10 minutes with a disperser. 22.32 g of PTFE dispersion was added to the obtained dispersion, followed by stirring for 5 minutes, followed by filtration. Furthermore, it dried in 80 degreeC dryer for 1 hour, grind | pulverized by the mill, and obtained the powder A for gas diffusion layers.

(Production of Gas Diffusion Electrode)

8.7 ml of ethanol was added to 4 g of powder A for gas diffusion layers, and the mixture was kneaded to obtain a jelly type. This jelly-like gas diffusion layer powder was molded into a sheet by a roll forming machine, and a silver mesh (SW = 1, LW = 2, thickness = 0.3 mm) was embedded as a current collector and finally molded into a 1.8 mm sheet. . 2.2 ml of ethanol was added to 1 g of the powder A for the reaction layer, and kneaded to obtain a jelly type. The jelly-like reaction layer powder was molded into a sheet of 0.2 mm in thickness by a roll molding machine. Moreover, two sheets of the sheet | seat obtained using the produced powder A for gas diffusion layers, and the sheet | seat obtained using the powder A for reaction layers were laminated | stacked, and it shape | molded in the sheet shape of 1.8 mm with the roll molding machine. This laminated sheet was dried for one day only at room temperature, and ethanol was removed. In addition, in order to remove the remaining surfactant, pyrolysis treatment was performed at 300 ° C. for 1 hour in air. Wrapped with aluminum foil, hot press was performed at 360 degreeC and 50 kgf / cm <2> for 1 minute with the hot press machine (SA303 (brand name), Tester Industry Co., Ltd.), and the gas diffusion electrode was obtained. The thickness of the gas diffusion electrode was 412 μm.

Electrolytic evaluation was performed using the obtained electrode. The cross-sectional structure of the electrolytic cell is arranged in the order of the current collector, the mattress, the nickel mesh feeder, the electrode, the film, and the anode from the cathode chamber side to form a zero gap structure. The results are shown in Table 7.

When the deformation | transformation test of the electrode was done, the average value of L <_1> , L <_2> was 19 mm.

The ventilation resistance of the electrode was measured, and found to be 25.88 (kPa · s / m) under measurement condition 1.

Moreover, handling property had a problem with "3". Moreover, when electrolytic evaluation was performed, current efficiency was low, the salt concentration in caustic soda became high, and electrolytic performance fell remarkably. Membrane damage evaluation also had a problem with "3".

From these results, it turned out that when the gas diffusion electrode obtained by the comparative example 4-1 is used, electrolytic performance will deteriorate remarkably. In addition, damage was observed on almost the entire surface of the ion exchange membrane. This was considered to be due to the fact that NaOH generated at the electrode stayed at the interface between the electrode and the diaphragm and had a high concentration because the airflow resistance of the gas diffusion electrode of Comparative Example 4-1 was remarkably large.

TABLE 6

TABLE 7

In Table 7, before the measurement of the "force applied per unit mass and unit area" and the "force applied per unit mass and unit area (2)" in all the samples, they were self-supporting by surface tension (i.e., flow Did not get off).

<Verification of the fifth embodiment>

As described below, an experimental example corresponding to the fifth embodiment (hereinafter simply referred to as "an example" in the section of <Verification of the fifth embodiment>) and an experimental example not corresponding to the fifth embodiment (Hereinafter, simply referred to as "comparative example" in the section of <Verification of Fifth Embodiment>) were prepared, and these were evaluated by the following method. The detail is demonstrated, referring FIGS. 93-94 and 100-102 suitably.

As a diaphragm, the ion exchange membrane A manufactured as follows was used.

As a reinforcing core material, it was made of polytetrafluoroethylene (PTFE) and 90 denier monofilament was used (hereinafter referred to as PTFE company). As the sacrificial yarn, a yarn in which twisted polyethylene denephthalate (PET) of 35 deniers and 6 filaments was applied 200 times / m was used (hereinafter referred to as PET yarn). First, in each of the two directions of TD and MD, the woven fabric was plain so that two lines of PTFE yarn were disposed between 24 lines / inch and two sacrificed yarns were adjacent to adjacent PTFE yarns. The obtained woven fabric was crimped with a roll to obtain a woven fabric having a thickness of 70 µm.

Next, Resin A, CF ₂ = CF ₂ , a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ , having an ion exchange capacity of 0.85 mg equivalent / g. And Resin B of a dry resin having a copolymer of CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and having an ion exchange capacity of 1.03 mg equivalent / g.

Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 µm and a resin B layer of 104 µm was obtained by a coextrusion T die method.

Subsequently, a hot plate having a heating source and a vacuum source therein and having fine holes on its surface was laminated in the order of release paper (conical embossing having a height of 50 μm), reinforcing material and film X, and hot plate. After heating and pressure-reducing for 2 minutes on the conditions of surface temperature 223 degreeC, and the pressure reduction degree 0.067 MPa, the composite film was obtained by removing a release paper.

The obtained composite membrane was saponified by immersing for 20 minutes in 80 degreeC aqueous solution containing 30 mass% of dimethyl sulfoxide (DMSO), and 15 mass% of potassium hydroxide (KOH). Then, it was immersed in 50 degreeC aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour, the counter ion of the ion exchange group was substituted by Na, and it washed with water continuously. Furthermore, it dried at 60 degreeC.

Further, a suspension obtained by adding 20 mass% of zirconium oxide having a primary particle size of 1 μm to a 5 mass% ethanol solution of the acid-type resin of the resin B was dispersed, sprayed onto both surfaces of the composite membrane by a suspension spray method, and A coating was formed on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconium oxide was 0.5 mg / cm 2 as measured by fluorescence X-ray measurement. Here, the average particle diameter was measured by the particle size distribution meter ("SALD (trademark) 2200" made by Shimadzu Corporation).

As the electrode, the following negative electrode and positive electrode were used.

As an electrode base material for negative electrode electrolysis, the electrolytic nickel foil whose gauge thickness is 22 micrometers was prepared. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. The arithmetic mean roughness Ra of the roughened surface was 0.95 탆. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted.

A circular hole was drilled into this nickel foil by punching to obtain a porous foil. The porosity was 44%.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of the produced electrode was 29 micrometers. The thickness of the catalyst layer containing ruthenium oxide and cerium oxide was 7 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side.

A titanium nonwoven fabric having a gauge thickness of 100 µm, a titanium fiber diameter of about 20 µm, a basis weight of 100 g / m 2, and a porosity of 78% was used as the electrode substrate for anode electrolysis.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. Ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L, iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) with a iridium concentration of 100 g / L, titanium tetrachloride (Wakkoyaku Industry Co., Ltd.), ruthenium element and iridium It mixed so that the molar ratio of an element and a titanium element might be 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred to prepare a positive electrode coating solution.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). After apply | coating the said coating liquid to titanium porous foil, it dried for 10 minutes at 60 degreeC, and baked for 10 minutes at 475 degreeC. After repeating these series of application | coating, drying, plasticity, and baking a series of operations, it baked at 520 degreeC for 1 hour.

Example 5-1

(Example using a cathode-film laminate)

The wound body was produced in advance as follows. First, the ion exchange membrane of 1.5 m in length and 2.5 m in width was prepared by the method described above. In addition, four negative electrodes having a length of 0.3 m and a width of 2.4 m were prepared by the method described above.

After immersing the ion exchange membrane in a 2% sodium bicarbonate solution for one day only, the negative electrode was arranged on the carboxylic acid layer side without a gap to prepare a laminate of the negative electrode and the ion exchange membrane (see FIG. 100). When the cathode was placed on the membrane, the interfacial tension acted upon contact with the aqueous sodium bicarbonate solution, and the membrane was adsorbed to integrate the cathode and the membrane. No pressure was applied when integrating in this manner. In addition, the temperature at the time of integration was 23 degreeC. As shown in FIG. 101, the obtained laminated body was wound by the polyvinyl chloride (PVC) pipe of outer diameter 76mm and length 1.7m, and the winding body was produced. The size of the wound body was a cylindrical shape having an outer diameter of 84 mm and a length of 1.7 m, and the laminate could be downsized.

Subsequently, in the existing large electrolytic cell (electrolyzer having the same structure as shown in FIGS. 93 and 94), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine is released, and the existing diaphragm is taken out and spaced between the electrolytic cells. I was in this state. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound laminated body could be taken out from the state which stood the PVC pipe. At this time, the laminate was held substantially perpendicular to the ground, but the cathode did not peel off and fall off. Subsequently, after inserting a laminated body between electrolytic cells, electrolytic cells were moved and the electrolytic cells were sandwiched.

Compared with the past, the electrode and the diaphragm could be replaced easily. When the wound body of a laminated body was prepared in advance during an electrolytic operation, it was evaluated that electrode update and diaphragm replacement can be completed for several tens of minutes per cell.

Example 5-2

(Example using an anode-film laminate)

The wound body was produced in advance as follows. First, the ion exchange membrane of 1.5 m in length and 2.5 m in width was prepared by the method described above. In addition, four positive electrodes having a length of 0.3 m and a width of 2.4 m were prepared by the method described above.

After immersing the ion exchange membrane in a 2% sodium bicarbonate solution for one day, the anodes were arranged on the sulfonic acid layer side in the same manner as in Example 5-1 without a gap to prepare a laminate of the anode and the ion exchange membrane. When the cathode was placed on the membrane, the interfacial tension acted upon contact with the aqueous sodium bicarbonate solution, and the membrane was adsorbed to integrate the cathode and the membrane. No pressure was applied when integrating in this manner. In addition, the temperature at the time of integration was 23 degreeC. The obtained laminated body was wound to the polyvinyl chloride (PVC) pipe of outer diameter 76mm and length 1.7m by the same method as Example 5-1, and the winding body was produced. The size of the wound body became a cylindrical shape having an outer diameter of 86 mm and a length of 1.7 m, and the laminate could be downsized.

Subsequently, in the existing large electrolytic cell (the same electrolytic cell as in Example 5-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine is released, and the existing diaphragm is taken out to have a gap between the electrolytic cells. did. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound laminated body could be taken out from the state which stood the PVC pipe. At this time, the laminate was held substantially perpendicular to the ground, but the anode did not peel off and fall off. Subsequently, after inserting a laminated body between electrolytic cells, electrolytic cells were moved and the electrolytic cells were sandwiched.

Compared with the past, the electrode and the diaphragm could be replaced easily. When the wound body of a laminated body was prepared in advance during an electrolytic operation, it was evaluated that electrode update and diaphragm replacement can be completed for several tens of minutes per cell.

Example 5-3

(Example using an anode / cathode-film laminate)

The wound body was produced in advance as follows. First, the ion exchange membrane of 1.5 m in length and 2.5 m in width was prepared by the method described above. In addition, four positive electrodes and a positive electrode each having a length of 0.3 m and a width of 2.4 m were prepared by the method described above.

After immersing the ion exchange membrane in a 2% sodium bicarbonate solution for one day only, the cathode was arranged on the carboxylic acid layer side and the anode was placed on the sulfonic acid layer side without a gap in the same manner as in Example 5-1. The laminated body was produced. When the negative electrode and the positive electrode were placed on the membrane, the interfacial tension acted upon contact with the aqueous sodium bicarbonate solution and was adsorbed to unite the negative electrode, the positive electrode and the membrane. No pressure was applied when integrating in this manner. In addition, the temperature at the time of integration was 23 degreeC. The obtained laminated body was wound to the polyvinyl chloride (PVC) pipe of outer diameter 76mm and length 1.7m by the same method as Example 5-1, and the winding body was produced. The size of the wound body became a cylindrical shape having an outer diameter of 88 mm and a length of 1.7 m, and the laminate could be downsized.

Subsequently, in the existing large electrolytic cell (the same electrolytic cell as in Example 5-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine is released, and the existing diaphragm is taken out to have a gap between the electrolytic cells. did. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound laminated body could be taken out from the state which stood the PVC pipe. At this time, the laminate was held substantially perpendicular to the ground, but the anode did not peel off and fall off. Subsequently, after inserting a laminated body between electrolytic cells, electrolytic cells were moved and the electrolytic cells were sandwiched.

Compared with the past, the electrode and the diaphragm could be replaced easily. When the wound body of a laminated body was prepared in advance during an electrolytic operation, it was evaluated that electrode update and diaphragm replacement can be completed for several tens of minutes per cell.

Example 5-4

(Example using a cathode)

The wound body was produced in advance as follows. First, four negative electrodes having a length of 0.3 m and a width of 2.4 m were prepared by the method described above. Four cathodes were arranged without a gap so that they were 1.2 m long and 2.4 m wide. As shown in FIG. 102, adjacent cathodes were bonded and fixed by passing a string of PTFE through the opening part (not shown) of a cathode so that a cathode may not fall. In this operation, no pressure was applied and the temperature was 23 ° C. The cathode was wound on a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m in the same manner as in Example 5-1 to prepare a wound body. The size of the wound body was a cylindrical shape having an outer diameter of 78 mm and a length of 1.7 m, and the laminate could be downsized.

Subsequently, in the existing large electrolytic cell (the same electrolytic cell as in Example 5-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine is released, and the existing diaphragm is taken out so that there are voids between the electrolytic cells. did. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound cathode could be drawn out from the state of the PVC pipe standing. At this time, the cathode was held substantially perpendicular to the ground, but the cathode did not peel off and fall off. Subsequently, after inserting a negative electrode between electrolytic cells, an electrolytic cell was moved and the electrolytic cells were sandwiched.

Compared with the conventional one, the negative electrode could be easily exchanged. When the negative electrode winding body was prepared in advance during the electrolytic operation, it was evaluated that the updating of the negative electrode could be completed for several tens of minutes per cell.

Example 5-5

(Example using the anode)

The wound body was produced in advance as follows. First, four positive electrodes having a length of 0.3 m and a width of 2.4 m were prepared by the method described above. Four anodes were arranged without gaps so that they were 1.2 m long and 2.4 m wide. In order to prevent the anodes from falling off, the anodes adjacent to each other were bonded to each other by a string of PTFE in the same manner as in Example 5-4. In this operation, no pressure was applied and the temperature was 23 ° C. The positive electrode was wound on a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m in the same manner as in Example 5-1 to prepare a wound body. The size of the wound body became a cylindrical shape with an outer diameter of 81 mm and a length of 1.7 m, and the laminate could be downsized.

Subsequently, in the existing large electrolytic cell (the same electrolytic cell as in Example 5-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine is released, and the existing diaphragm is taken out to have a gap between the electrolytic cells. did. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound positive electrode could be taken out from the state which stood the PVC pipe. At this time, the anode was held substantially perpendicular to the ground, but the anode did not peel off and fall off. Subsequently, after inserting an anode between electrolytic cells, an electrolytic cell was moved and the electrolytic cells were sandwiched.

Compared with the past, the anodes could be easily exchanged. If the positive electrode winding body was prepared in advance during the electrolytic operation, it was estimated that the update of the positive electrode could be completed for several tens of minutes per cell.

Comparative Example 5-1

(Conventional electrode update)

In the existing large electrolytic cell (the same electrolytic cell as Example 5-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by a press machine was canceled, the existing diaphragm was taken out, and it was set as the state which has a space | gap between electrolytic cells. Then, the electrolysis cell was suspended by the hoist from the large electrolytic cell. The electrolytic cell taken out was carried to the factory which can be welded.

After the positive electrode fixed to the rib of the electrolysis cell was removed by welding, the burr etc. of the part removed using the grinder etc. were shaved and smoothed. The negative electrode peeled off the fixed part which was put in the collector and fixed.

Thereafter, a new anode was installed on the rib of the anode chamber, and the new anode was fixed to the electrolytic cell by spot welding. Similarly, a new negative electrode was installed on the negative electrode side and fixed in a current collector.

The electrolysis cell after completion of the renewal was transported to the place of the large electrolytic cell, and the electrolytic cell was returned to the electrolytic cell using a hoist.

The time required for releasing the fixation state of the electrolysis cell and the ion exchange membrane and then fixing the electrolysis cell again was 1 day or more.

<Verification of the Sixth Embodiment>

As described below, an experimental example corresponding to the sixth embodiment (hereinafter simply referred to as "an example" in the section of <Verification of the sixth embodiment>) and an experimental example not corresponding to the sixth embodiment (Simply referred to as "comparative example" in the following section in <Verification of Sixth Embodiment>) was prepared, and these were evaluated by the following method. The details will be described with reference to FIGS. 105 to 106 as appropriate.

As a diaphragm, the ion exchange membrane b manufactured as follows was used.

As a reinforcing core material, it was made of polytetrafluoroethylene (PTFE) and 90 denier monofilament was used (hereinafter referred to as PTFE company). As the sacrificial yarn, a yarn in which twisted polyethylene denephthalate (PET) of 35 deniers and 6 filaments was applied 200 times / m was used (hereinafter referred to as PET yarn). First, in each of the two directions of TD and MD, the woven fabric was plain so that two lines of PTFE yarn were disposed between 24 lines / inch and two sacrificed yarns were adjacent to adjacent PTFE yarns. The obtained woven fabric was crimped with a roll to obtain a woven fabric having a thickness of 70 µm.

Next, Resin A, CF ₂ = CF ₂ , a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ , having an ion exchange capacity of 0.85 mg equivalent / g. And Resin B of a dry resin having a copolymer of CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and having an ion exchange capacity of 1.03 mg equivalent / g.

Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 µm and a resin B layer of 104 µm was obtained by a coextrusion T die method.

Subsequently, a hot plate having a heating source and a vacuum source therein and having fine holes on its surface was laminated in the order of release paper (conical embossing having a height of 50 μm), reinforcing material and film X, and hot plate. After heating and pressure-reducing for 2 minutes on the conditions of surface temperature 223 degreeC, and the pressure reduction degree 0.067 MPa, the composite film was obtained by removing a release paper.

The obtained composite membrane was saponified by immersing for 20 minutes in 80 degreeC aqueous solution containing 30 mass% of dimethyl sulfoxide (DMSO), and 15 mass% of potassium hydroxide (KOH). Then, it was immersed in the 50 degreeC aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour, the counter ion of the ion exchanger was substituted by Na, and water washing was continued. Furthermore, it dried at 60 degreeC.

Further, a suspension obtained by adding 20 mass% of zirconium oxide having a primary particle size of 1 μm to a 5 mass% ethanol solution of the acid-type resin of the resin B was dispersed, sprayed onto both surfaces of the composite membrane by a suspension spray method, and A coating was formed on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconium oxide was 0.5 mg / cm 2 as measured by fluorescence X-ray measurement. Here, the average particle diameter was measured by the particle size distribution meter ("SALD (trademark) 2200" made by Shimadzu Corporation).

As the electrode, the following negative electrode and positive electrode were used.

As an electrode base material for negative electrode electrolysis, the electrolytic nickel foil whose gauge thickness is 22 micrometers was prepared. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. The arithmetic mean roughness Ra of the roughened surface was 0.95 탆. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted.

A circular hole was drilled into this nickel foil by punching to obtain a porous foil. The porosity was 44%.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of the produced electrode was 29 micrometers. The thickness of the catalyst layer containing ruthenium oxide and cerium oxide was 7 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side.

A titanium nonwoven fabric having a gauge thickness of 100 µm, a titanium fiber diameter of about 20 µm, a basis weight of 100 g / m 2, and a porosity of 78% was used as the electrode substrate for anode electrolysis.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. Ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L, iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) with a iridium concentration of 100 g / L, titanium tetrachloride (Wakkoyaku Industry Co., Ltd.), ruthenium element and iridium It mixed so that the molar ratio of an element and a titanium element might be 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred to prepare a positive electrode coating solution.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). After apply | coating the said coating liquid to titanium porous foil, it dried for 10 minutes at 60 degreeC, and baked for 10 minutes at 475 degreeC. After repeating these series of application | coating, drying, plasticity, and baking a series of operations, it baked at 520 degreeC for 1 hour.

Example 6-1

(Example using a cathode-film laminate)

The wound body was produced in advance as follows. First, the ion exchange membrane b of 1.5 m in length and 2.5 m in width was prepared by the method described above. In addition, four negative electrodes having a length of 0.3 m and a width of 2.4 m were prepared by the method described above.

After immersing the ion exchange membrane b in a 2% sodium bicarbonate solution for one day, the negative electrode was arranged on the carboxylic acid layer side without a gap to prepare a laminate of the negative electrode and the ion exchange membrane b. When the cathode was placed on the membrane, the interfacial tension acted upon contact with the aqueous sodium bicarbonate solution, and the membrane was adsorbed to integrate the cathode and the membrane. No pressure was applied when integrating in this manner. In addition, the temperature at the time of integration was 23 degreeC. The laminate was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to produce a wound body. In addition, in order to melt the ion exchange membrane b, 200 degreeC or more is required, and when integrated in this Example, the ion exchange membrane did not melt.

Subsequently, in the existing large electrolytic cell (electrolyzer having the same structure as shown in FIGS. 105 and 106), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine is released, and the existing diaphragm is taken out and spaced between the electrolytic cells. I was in this state. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound laminated body could be taken out from the state which stood the PVC pipe. At this time, the laminate was held substantially perpendicular to the ground, but the cathode did not peel off and fall off. Subsequently, after inserting a laminated body between electrolytic cells, electrolytic cells were moved and the electrolytic cells were sandwiched.

Compared with the past, the electrode and the diaphragm could be replaced easily. It was evaluated that electrode update and diaphragm replacement can be completed in about several tens of minutes per cell.

Example 6-2

(Example using an anode-film laminate)

The wound body was produced in advance as follows. First, the ion exchange membrane b of 1.5 m in length and 2.5 m in width was prepared by the method described above. In addition, four positive electrodes having a length of 0.3 m and a width of 2.4 m were prepared by the method described above.

After immersing the ion exchange membrane b in a 2% sodium bicarbonate solution for one day, the anode was arranged on the sulfonic acid layer side without a gap to prepare a laminate of the anode and the ion exchange membrane. When the positive electrode was placed on the membrane, the interfacial tension acted upon contact with the aqueous sodium bicarbonate solution, and the positive electrode and the membrane were integrated. No pressure was applied when integrating in this manner. In addition, the temperature at the time of integration was 23 degreeC. The laminate was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to produce a wound body.

Subsequently, in the existing large electrolytic cell (the same electrolytic cell as in Example 6-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine is released, and the existing diaphragm is taken out to have a gap between the electrolytic cells. did. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound laminated body could be taken out from the state which stood the PVC pipe. At this time, the laminate was held substantially perpendicular to the ground, but the anode did not peel off and fall off. Subsequently, after inserting a laminated body between electrolytic cells, electrolytic cells were moved and the electrolytic cells were sandwiched.

Compared with the past, the electrode and the diaphragm could be replaced easily. It was evaluated that electrode update and diaphragm replacement can be completed in about several tens of minutes per cell.

Example 6-3

(Example using an anode / cathode-film laminate)

The wound body was produced in advance as follows. First, the ion exchange membrane b of 1.5 m in length and 2.5 m in width was prepared by the method described above. In addition, four positive electrodes and a positive electrode each having a length of 0.3 m and a width of 2.4 m were prepared by the method described above.

After immersing the ion exchange membrane b in a 2% sodium bicarbonate solution for one day, a cathode was arranged on the carboxylic acid layer side and an anode was arranged on the sulfonic acid layer side without a gap to prepare a laminate of the cathode, the anode, and the ion exchange membrane b. When the negative electrode and the positive electrode were placed on the membrane, the interfacial tension acted upon contact with the aqueous sodium bicarbonate solution, and they were adsorbed to unite the negative electrode, the positive electrode and the membrane. No pressure was applied when integrating in this manner. In addition, the temperature at the time of integration was 23 degreeC. The laminate was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to produce a wound body.

Subsequently, in the existing large electrolytic cell (the same electrolytic cell as in Example 6-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine is released, and the existing diaphragm is taken out to have a gap between the electrolytic cells. did. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound laminated body could be taken out from the state which stood the PVC pipe. At this time, the laminate was held substantially perpendicular to the ground, but the anode did not peel off and fall off. Subsequently, after inserting a laminated body between electrolytic cells, electrolytic cells were moved and the electrolytic cells were sandwiched.

Compared with the past, the electrode and the diaphragm could be replaced easily. It was evaluated that electrode update and diaphragm replacement can be completed in about several tens of minutes per cell.

Comparative Example 6-1

As described below, a membrane electrode laminate in which an electrode was thermocompression-bonded to a diaphragm was produced with reference to the example of JP-A-58-48686.

Electrode coating was carried out in the same manner as in Example 6-1, using a nickel expanded metal having a gauge thickness of 100 µm and a porosity of 33% as the electrode base material for cathode electrolysis. The size of the electrode was 200 mm x 200 mm, and the number of sheets was 72. Thereafter, one surface of the electrode was subjected to deactivation in the following order. A polyimide adhesive tape (Chuko Chemical Co., Ltd.) was adhered to one side of the electrode, and PTFE dispersion (Mitsui Dupont Floro Co., Ltd., 31-JR (trade name)) was applied to the opposite side, and dried in a muffle furnace at 120 ° C for 10 minutes. The polyimide tape was peeled off and the sintering process was performed for 10 minutes in the muffle furnace set to 380 degree C. This operation was repeated twice, and one side of the electrode was inactivated.

A film formed of two layers of a perfluorocarbon polymer (C polymer) having a terminal functional group of "-COOCH ₃ " and a perfluorocarbon polymer (S polymer) having a terminal group of "-SO ₂ F" was produced. The C polymer layer was 3 mils thick and the S polymer layer was 4 mils thick. The saponification process was performed to this two-layer film, and the ion exchanger was introduce | transduced by hydrolysis to the terminal of a polymer. The C polymer end was hydrolyzed to the carboxylic acid group and the S polymer end to the sulfo group. The ion exchange capacity as the sulfonic acid group was 1.0 meq / g, and the ion exchange capacity as the carboxylic acid group was 0.9 meq / g. The size of the obtained ion exchange membrane was the same as that of Example 6-1.

On the surface having a carboxylic acid group as an ion exchanger, the inactivated electrode surface of the electrode was opposed to perform a thermal press (thermocompression bonding) to integrate the ion exchange membrane and the electrode. That is, 72 sheets of 200 mm square electrodes were integrated with one ion exchange membrane having a length of 1500 mm and a width of 2500 mm at a temperature at which the ion exchange membrane was melted. Even after thermocompression bonding, one side of the electrode was exposed, and no part of the electrode penetrated the membrane.

In the large size of 1500 mm x 2500 mm, the process of integrating the ion exchange membrane and the electrode by thermocompression bonding required more than one day. That is, at the time of electrode update and replacement of a diaphragm, it evaluated that more time was needed in Comparative Example 6-1 than Example.

<Verification of the Seventh Embodiment>

As described below, an experimental example corresponding to the seventh embodiment (hereinafter simply referred to as "an example" in the section of <verification of the seventh embodiment>) and an experimental example not corresponding to the seventh embodiment (Hereinafter, simply referred to as "comparative example" in the following section in <Verification of the Seventh Embodiment>) were prepared, and these were evaluated by the following method. The details will be described with reference to FIGS. 114 to 115 as appropriate.

As a diaphragm, the ion exchange membrane manufactured as follows was used.

As a reinforcing core material, it was made of polytetrafluoroethylene (PTFE) and 90 denier monofilament was used (hereinafter referred to as PTFE company). As the sacrificial yarn, a yarn in which twisted polyethylene denephthalate (PET) of 35 deniers and 6 filaments was applied 200 times / m was used (hereinafter referred to as PET yarn). First, in each of the two directions of TD and MD, the woven fabric was plain so that two lines of PTFE yarn were disposed between 24 lines / inch and two sacrificed yarns were adjacent to adjacent PTFE yarns. The obtained woven fabric was crimped with a roll to obtain a woven fabric having a thickness of 70 µm.

Next, Resin A, CF ₂ = CF ₂ , a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ , having an ion exchange capacity of 0.85 mg equivalent / g. And Resin B of a dry resin having a copolymer of CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and having an ion exchange capacity of 1.03 mg equivalent / g.

Using these resins A and B, a two-layer film X having a thickness of the resin A layer of 15 µm and a resin B layer of 104 µm was obtained by a coextrusion T die method. Subsequently, a hot plate having a heating source and a vacuum source therein and having fine holes on its surface was laminated in the order of release paper (conical embossing having a height of 50 μm), reinforcing material and film X, and hot plate. After heating and pressure-reducing for 2 minutes on the conditions of surface temperature 223 degreeC, and the pressure reduction degree 0.067 MPa, the composite film was obtained by removing a release paper.

The obtained composite membrane was saponified by immersing for 20 minutes in 80 degreeC aqueous solution containing 30 mass% of dimethyl sulfoxide (DMSO), and 15 mass% of potassium hydroxide (KOH). Then, it was immersed in 50 degreeC aqueous solution containing 0.5 N of sodium hydroxide (NaOH) for 1 hour, the counter ion of the ion exchange group was substituted by Na, and it washed with water continuously. Furthermore, it dried at 60 degreeC.

Further, a suspension obtained by adding 20 mass% of zirconium oxide having a primary particle size of 1 μm to a 5 mass% ethanol solution of the acid-type resin of the resin B was dispersed, sprayed onto both surfaces of the composite membrane by a suspension spray method, and A coating was formed on the surface of the composite membrane to obtain an ion exchange membrane A. The coating density of zirconium oxide was 0.5 mg / cm 2 as measured by fluorescence X-ray measurement. Here, the average particle diameter was measured by the particle size distribution meter ("SALD (trademark) 2200" made by Shimadzu Corporation).

As the electrode, the following negative electrode and positive electrode were used.

As an electrode base material for negative electrode electrolysis, the electrolytic nickel foil whose gauge thickness is 22 micrometers was prepared. The roughening process by electrolytic nickel plating was given to one surface of this nickel foil. The arithmetic mean roughness Ra of the roughened surface was 0.95 탆. The measurement of the surface roughness was performed on the same conditions as the surface roughness measurement of the nickel plate which blasted.

A circular hole was drilled into this nickel foil by punching to obtain a porous foil. The porosity was 44%.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) and cerium nitrate (Kishida Chemical Co., Ltd.) having a ruthenium concentration of 100 g / L were mixed so that the molar ratio of the ruthenium element and the cerium element was 1: 0.25. This mixed liquid was sufficiently stirred to make this a negative electrode coating liquid.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying was performed at 50 ° C for 10 minutes, plasticity at 150 ° C for 3 minutes, and baking at 350 ° C for 10 minutes. A series of operations of coating, drying, plasticity and firing were repeated until a predetermined coating amount was obtained. The thickness of the produced electrode was 29 micrometers. The thickness of the catalyst layer containing ruthenium oxide and cerium oxide was 7 micrometers after subtracting the thickness of the electrode base material for electrolysis from the thickness of an electrode. The coating was also formed on the unroughened side.

A titanium nonwoven fabric having a gauge thickness of 100 µm, a titanium fiber diameter of about 20 µm, a basis weight of 100 g / m 2, and a porosity of 78% was used as the electrode substrate for anode electrolysis.

The coating liquid for forming an electrode catalyst was prepared in the following procedures. Ruthenium chloride solution (Tanaka Precious Metals Industry Co., Ltd.) with a ruthenium concentration of 100 g / L, iridium chloride (Tanaka Precious Metals Industry Co., Ltd.) with a iridium concentration of 100 g / L, titanium tetrachloride (Wakkoyaku Industry Co., Ltd.), ruthenium element and iridium It mixed so that the molar ratio of an element and a titanium element might be 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred to prepare a positive electrode coating solution.

The bat which put the said coating liquid was installed in the lowest part of a roll coating apparatus. A coating roll and a coating liquid wound around a rubber (Innoac Corporation, E-4088, thickness 10 mm) made of foamed EPDM (ethylene, propylene, diene rubber) of independent bubble type in a cylinder made of PVC (polyvinyl chloride) are always Installed to contact. The coating roll which wound the same EPDM was provided in the upper part, and the PVC roller was further installed on it. The coating solution was applied by passing the electrode base material between the second coating roll and the uppermost PVC roller (roll coating method). After apply | coating the said coating liquid to titanium porous foil, it dried for 10 minutes at 60 degreeC, and baked for 10 minutes at 475 degreeC. After repeating these series of application | coating, drying, plasticity, and baking a series of operations, it baked at 520 degreeC for 1 hour.

Example 7-1

(Example using a cathode-film laminate)

The wound body was produced in advance as follows. First, the ion exchange membrane of 1.5 m in length and 2.5 m in width was prepared by the method described above. In addition, four negative electrodes having a length of 0.3 m and a width of 2.4 m were prepared by the method described above.

After immersing the ion exchange membrane in a 2% sodium bicarbonate solution for one day only, the negative electrode was arranged on the carboxylic acid layer side without a gap to prepare a laminate of the negative electrode and the ion exchange membrane. When the cathode was placed on the membrane, the interfacial tension acted upon contact with the aqueous sodium bicarbonate solution, and the membrane was adsorbed to integrate the cathode and the membrane. No pressure was applied when integrating in this manner. In addition, the temperature at the time of integration was 23 degreeC. The laminate was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to produce a wound body.

Subsequently, in the existing large electrolytic cell (electrolyzer having the same structure as shown in FIGS. 114 and 115), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine is released, and the existing diaphragm is taken out and the space between the electrolytic cells is removed. I was in this state. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound laminated body could be taken out from the state which stood the PVC pipe. At this time, the laminate was held substantially perpendicular to the ground, but the cathode did not peel off and fall off. Subsequently, after inserting a laminated body between electrolytic cells, electrolytic cells were moved and the electrolytic cells were sandwiched.

Compared with the past, the electrode and the diaphragm could be replaced easily. When the wound body of a laminated body was prepared in advance during an electrolytic operation, it was evaluated that electrode update and diaphragm replacement can be completed for several tens of minutes per cell.

Example 7-2

(Example using an anode-film laminate)

The wound body was produced in advance as follows. First, the ion exchange membrane of 1.5 m in length and 2.5 m in width was prepared by the method described above. In addition, four positive electrodes having a length of 0.3 m and a width of 2.4 m were prepared by the method described above.

After immersing the ion exchange membrane in a 2% sodium bicarbonate solution for one day, the anodes were arranged on the sulfonic acid layer side without any gaps to prepare a laminate of the anode and the ion exchange membrane. When the anode was placed on the membrane, the interfacial tension acted upon contact with the aqueous sodium bicarbonate solution, and the membrane was adsorbed to unite the anode and the membrane. No pressure was applied when integrating in this way. In addition, the temperature at the time of integration was 23 degreeC. The laminate was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to produce a wound body.

Subsequently, in the existing large electrolytic cell (the same electrolytic cell as in Example 7-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press is released, and the existing diaphragm is taken out so that there is a gap between the electrolytic cells. did. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound laminated body could be taken out from the state which stood the PVC pipe. At this time, the laminate was held substantially perpendicular to the ground, but the anode did not peel off and fall off. Subsequently, after inserting a laminated body between electrolytic cells, electrolytic cells were moved and the electrolytic cells were sandwiched.

Compared with the past, the electrode and the diaphragm could be replaced easily. When the wound body of a laminated body was prepared in advance during an electrolytic operation, it was evaluated that electrode update and diaphragm replacement can be completed for several tens of minutes per cell.

Example 7-3

(Example using an anode / cathode-film laminate)

The wound body was produced in advance as follows. First, the ion exchange membrane of 1.5 m in length and 2.5 m in width was prepared by the method described above. In addition, four positive electrodes and a positive electrode each having a length of 0.3 m and a width of 2.4 m were prepared by the method described above.

After immersing the ion exchange membrane in a 2% sodium bicarbonate solution for one day only, the negative electrode was arranged on the carboxylic acid layer side and the positive electrode was arranged without the gap on the sulfonic acid layer side, to prepare a laminate of the negative electrode, the positive electrode and the ion exchange membrane. When the negative electrode and the positive electrode were placed on the membrane, the interfacial tension acted upon contact with the aqueous sodium bicarbonate solution, and they were adsorbed to unite the negative electrode, the positive electrode and the membrane. No pressure was applied when integrating in this manner. In addition, the temperature at the time of integration was 23 degreeC. The laminate was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to produce a wound body.

Subsequently, in the existing large electrolytic cell (the same electrolytic cell as in Example 7-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press is released, and the existing diaphragm is taken out so that there is a gap between the electrolytic cells. did. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound laminated body could be taken out from the state which stood the PVC pipe. At this time, the laminate was held substantially perpendicular to the ground, but the anode did not peel off and fall off. Subsequently, after inserting a laminated body between electrolytic cells, electrolytic cells were moved and the electrolytic cells were sandwiched.

Compared with the past, the electrode and the diaphragm could be replaced easily. When the wound body of a laminated body was prepared in advance during an electrolytic operation, it was evaluated that electrode update and diaphragm replacement can be completed for several tens of minutes per cell.

Example 7-4

(Example using a cathode)

The wound body was produced in advance as follows. First, four negative electrodes having a length of 0.3 m and a width of 2.4 m were prepared by the method described above. Four cathodes were arranged without a gap so that they were 1.2 m long and 2.4 m wide. Adjacent negative electrodes were bonded and fixed with a string of PTFE so that the negative electrodes did not fall off. In this operation, no pressure was applied and the temperature was 23 ° C. This cathode was wound around a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to produce a wound body.

Subsequently, in the existing large electrolytic cell (the same electrolytic cell as in Example 7-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press is released, and the existing diaphragm is taken out so that there is a gap between the electrolytic cells. did. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound cathode could be drawn out from the state of the PVC pipe standing. At this time, the cathode was held substantially perpendicular to the ground, but the cathode did not peel off and fall off. Subsequently, after inserting a negative electrode between electrolytic cells, an electrolytic cell was moved and the electrolytic cells were sandwiched.

Compared with the conventional one, the negative electrode could be easily exchanged. When the negative electrode winding body was prepared in advance during the electrolytic operation, it was evaluated that the updating of the negative electrode could be completed for several tens of minutes per cell.

Example 7-5

(Example using the anode)

The wound body was produced in advance as follows. First, four positive electrodes having a length of 0.3 m and a width of 2.4 m were prepared by the method described above. Four anodes were arranged without gaps so that they were 1.2 m long and 2.4 m wide. The anodes adjacent to each other were bonded and fixed with a string of PTFE so that the anodes did not fall off. In this operation, no pressure was applied and the temperature was 23 ° C. This anode was wound up to a polyvinyl chloride (PVC) pipe having an outer diameter of 76 mm and a length of 1.7 m to produce a wound body.

Subsequently, in the existing large electrolytic cell (the same electrolytic cell as in Example 7-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press is released, and the existing diaphragm is taken out so that there is a gap between the electrolytic cells. did. Thereafter, the wound body was transferred onto a large electrolytic cell. On a large electrolytic cell, the wound state was canceled so that the wound positive electrode could be taken out from the state which stood the PVC pipe. At this time, the anode was held substantially perpendicular to the ground, but the anode did not peel off and fall off. Subsequently, after inserting an anode between electrolytic cells, an electrolytic cell was moved and the electrolytic cells were sandwiched.

Compared with the past, the anodes could be easily exchanged. If the positive electrode winding body was prepared in advance during the electrolytic operation, it was estimated that the update of the positive electrode could be completed for several tens of minutes per cell.

Comparative Example 7-1

(Conventional electrode update)

In the existing large electrolytic cell (the same electrolyzer as in Example 7-1), the fixing state of the adjacent electrolytic cell and the ion exchange membrane by the press machine was released, the existing diaphragm was taken out, and the space | gap existed between electrolytic cells. Then, the electrolysis cell was suspended by the hoist from the large electrolytic cell. The electrolytic cell taken out was carried to the factory which can be welded.

After the positive electrode fixed to the rib of the electrolysis cell was removed by welding, the burr etc. of the part removed using the grinder etc. were shaved and smoothed. The negative electrode peeled off the fixed part which was put in the collector and fixed.

Thereafter, a new anode was installed on the rib of the anode chamber, and the new anode was fixed to the electrolytic cell by spot welding. Similarly, a new negative electrode was installed on the negative electrode side and fixed in a current collector.

The electrolysis cell after completion of the renewal was transported to the place of the large electrolytic cell, and the electrolytic cell was returned to the electrolytic cell using a hoist.

The time required for releasing the fixation state of the electrolysis cell and the ion exchange membrane and then fixing the electrolysis cell again was 1 day or more.

This application is a Japanese patent application (No. 2017-056524 and 2017-056525) of an application on March 22, 2017, and a Japanese patent application (2018-053217, 2018-) of an application on March 20, 2018. 053146, 2018-053144, 2018-053231, 2018-053145, 2018-053149, and 2018-053139), the contents of which are incorporated herein by reference.

<Figure corresponding to the first embodiment>
Explanation of the code | symbol for FIG.
10: electrode base for electrolysis, 20: first layer, 30: second layer, 100: electrode for electrolysis.
Explanation of the code | symbol about FIGS. 2-4
DESCRIPTION OF REFERENCE NUMERALS 1: ion exchange membrane, 2: carboxylic acid layer, 3: sulfonic acid layer, 4: reinforced core material, 10: membrane body, 11a, 11b: coating layer, 21, 22: reinforced core material, 100: electrolytic cell, 200: positive electrode, 300: negative electrode , 52: reinforcer, 504a: victim, 504: communication hole.
Explanation of the code | symbol about FIGS. 5-9
Reference Signs List 1 electrolytic cell, 2 ion exchange membrane, 4 electrolyzer, 5 press machine, 6 cathode terminal, 7 anode terminal, 10 anode chamber, 11 anode, 12 anode gasket, 13 cathode gasket, 18 reverse Rather absorber, 18a: base material, 18b: reverse current absorbing layer, 19: bottom of anode chamber, 20: cathode chamber, 21: cathode, 22: metal elastic body, 23: current collector, 24: support, 30: partition, 40: Electrolytic Cathode Structure.
Explanation of the code | symbol for FIG.
DESCRIPTION OF SYMBOLS 1 Punching jig (SUS), 2: Electrode, 3: Diaphragm, 4: Nickel plate (Alumina blasting of particle number 320), 100: Front, 200: Side.
Explanation of the code | symbol about FIGS. 11-13
1: diaphragm, 2a: polyethylene pipe having an outer diameter of 280 mm, 2b: polyethylene pipe having an outer diameter of 145 mm, 3: peeling portion, 4: adhesion portion, 5: electrode.
Explanation of the code | symbol about FIG.
1: PVC (polyvinyl chloride) pipe, 2: ion exchange membrane, 3: electrode, 4: table
Explanation of the code | symbol for FIG.
1: plate, 2: deformed electrode, 10: jig fixing the electrode, 20: direction of applying force
Explanation of the code | symbol about FIGS. 16-21
1: 110 mm nickel wire, 2: 950 mm nickel wire, 3: frame
<Figure corresponding to the second embodiment>
Explanation of the code | symbol about FIG.
10: electrode base for electrolysis, 20: first layer, 30: second layer, 100: electrode for electrolysis.
Explanation of the code | symbol about FIGS. 23-25
DESCRIPTION OF REFERENCE NUMERALS 1: ion exchange membrane, 2: carboxylic acid layer, 3: sulfonic acid layer, 4: reinforced core material, 10: membrane body, 11a, 11b: coating layer, 21, 22: reinforced core material, 100: electrolytic cell, 200: positive electrode, 300: negative electrode , 52: reinforcer, 504a: victim, 504: communication hole.
Explanation of the code | symbol about FIGS. 26-30
Reference Signs List 1 electrolytic cell, 2 ion exchange membrane, 4 electrolyzer, 5 press machine, 6 cathode terminal, 7 anode terminal, 10 anode chamber, 11 anode, 12 anode gasket, 13 cathode gasket, 18 reverse Rather absorber, 18a: base material, 18b: reverse current absorbing layer, 19: bottom of anode chamber, 20: cathode chamber, 21: cathode, 22: metal elastic body, 23: current collector, 24: support, 30: partition, 40: Electrolytic Cathode Structure.
Explanation of the code | symbol about FIG.
DESCRIPTION OF SYMBOLS 1 Punching jig (SUS), 2: Electrode, 3: Diaphragm, 4: Nickel plate (Alumina blasting of particle number 320), 100: Front, 200: Side.
Explanation of the code | symbol about FIGS. 32-34
1: diaphragm, 2a: polyethylene pipe having an outer diameter of 280 mm, 2b: polyethylene pipe having an outer diameter of 145 mm, 3: peeling portion, 4: adhesion portion, 5: electrode.
Explanation of the code | symbol for FIG. 35
1: PVC (polyvinyl chloride) pipe, 2: ion exchange membrane, 3: electrode, 4: table
Explanation of the code | symbol about FIG. 36
1: plate, 2: deformed electrode, 10: jig fixing the electrode, 20: direction of applying force
Explanation of the code | symbol about FIGS. 37-42
1: 110 mm nickel wire, 2: 950 mm nickel wire, 3: frame
<Figure corresponding to the third embodiment>
Explanation of the code | symbol about FIG. 43
10: electrode base for electrolysis, 20: first layer, 30: second layer, 100: electrode for electrolysis.
Explanation of the code | symbol about FIGS. 44-46
DESCRIPTION OF REFERENCE NUMERALS 1: ion exchange membrane, 2: carboxylic acid layer, 3: sulfonic acid layer, 4: reinforced core material, 10: membrane body, 11a, 11b: coating layer, 21, 22: reinforced core material, 100: electrolytic cell, 200: positive electrode, 300: negative electrode , 52: reinforcer, 504a: victim, 504: communication hole.
Explanation of the code | symbol about FIGS. 47-51
DESCRIPTION OF SYMBOLS 1 Laminated body 2 Electrode electrode for electrolysis 2a Inner surface of electrode for electrolysis 2b Outer surface of electrode for electrolysis 3 Diaphragm 3a Inner surface of diaphragm 3b Outer surface of diaphragm 7 Fixed Absence.
Explanation of the code | symbol about FIGS. 52-56
Reference Signs List 1 electrolytic cell, 2 ion exchange membrane, 4 electrolyzer, 5 press machine, 6 cathode terminal, 7 anode terminal, 10 anode chamber, 11 anode, 12 anode gasket, 13 cathode gasket, 18 reverse Rather absorber, 18a: base material, 18b: reverse current absorbing layer, 19: bottom of anode chamber, 20: cathode chamber, 21: cathode, 22: metal elastic body, 23: current collector, 24: support, 30: partition, 40: Electrolytic Cathode Structure.
<Figure corresponding to the fourth embodiment>
Explanation of the code | symbol about FIGS. 63-67
Reference Signs List 1 electrolytic cell, 2 ion exchange membrane, 4 electrolyzer, 5 press machine, 6 cathode terminal, 7 anode terminal, 10 anode chamber, 11 anode, 12 anode gasket, 13 cathode gasket, 18 reverse Rather absorber, 18a: base material, 18b: reverse current absorbing layer, 19: bottom of anode chamber, 20: cathode chamber, 21: cathode, 22: metal elastic body, 23: current collector, 24: support, 30: partition, 40: Electrolytic Cathode Structure.
Explanation of the code | symbol about FIG. 68
10: electrode base for electrolysis, 20: first layer, 30: second layer, 100: electrode for electrolysis.
Explanation of the code | symbol about FIGS. 69-71
DESCRIPTION OF REFERENCE NUMERALS 1: ion exchange membrane, 2: carboxylic acid layer, 3: sulfonic acid layer, 4: reinforced core material, 10: membrane body, 11a, 11b: coating layer, 21, 22: reinforced core material, 100: electrolytic cell, 200: positive electrode, 300: negative electrode , 52: reinforcer, 504a: victim, 504: communication hole.
Explanation of the code | symbol about FIGS. 72-78
DESCRIPTION OF SYMBOLS 1 Laminated body 2 Electrode electrode for electrolysis 2a Inner surface of electrode for electrolysis 2b Outer surface of electrode for electrolysis 3 Diaphragm 3a Inner surface of diaphragm 3b Outer surface of diaphragm 7 Fixed Member, A: gasket, B: diaphragm, C: electrode for electrolysis, A1: outermost edge of the gasket, B1: outermost edge of the diaphragm, C1: outermost edge of the electrode for electrolysis.
Explanation of the code | symbol about FIG. 79
DESCRIPTION OF SYMBOLS 1 Punching jig (SUS), 2: Electrode, 3: Diaphragm, 4: Nickel plate (Alumina blasting of particle number 320), 100: Front, 200: Side.
Explanation of the code | symbol about FIGS. 80-82
1: diaphragm, 2a: polyethylene pipe having an outer diameter of 280 mm, 2b: polyethylene pipe having an outer diameter of 145 mm, 3: peeling portion, 4: adhesion portion, 5: electrode.
Explanation of the code | symbol about FIG. 84
1: plate, 2: deformed electrode, 10: jig fixing the electrode, 20: direction of applying force
Explanation of the code | symbol about FIGS. 85-90
1: 110 mm nickel wire, 2: 950 mm nickel wire, 3: frame
<Figure corresponding to the fifth embodiment>
Explanation of the code | symbol about FIGS. 91-95
Reference Signs List 1 electrolytic cell, 2 ion exchange membrane, 4 electrolyzer, 5 press machine, 6 cathode terminal, 7 anode terminal, 10 anode chamber, 11 anode, 12 anode gasket, 13 cathode gasket, 18 reverse Rather absorber, 18a: base material, 18b: reverse current absorbing layer, 19: bottom of anode chamber, 20: cathode chamber, 21: cathode, 22: metal elastic body, 23: current collector, 24: support, 30: partition, 40: Electrolytic Cathode Structure.
Explanation of the code | symbol about FIG. 96
10: electrode base for electrolysis, 20: first layer, 30: second layer, 100: electrode for electrolysis.
Explanation of the code | symbol about FIGS. 97-99
DESCRIPTION OF REFERENCE NUMERALS 1: ion exchange membrane, 2: carboxylic acid layer, 3: sulfonic acid layer, 4: reinforced core material, 10: membrane body, 11a, 11b: coating layer, 21, 22: reinforced core material, 100: electrolytic cell, 200: positive electrode, 300: negative electrode , 52: reinforcer, 504a: victim, 504: communication hole.
<Figure corresponding to the sixth embodiment>
Explanation of the reference numerals for FIGS. 103 to 107
Reference Signs List 1 electrolytic cell, 2 ion exchange membrane, 4 electrolyzer, 5 press machine, 6 cathode terminal, 7 anode terminal, 10 anode chamber, 11 anode, 12 anode gasket, 13 cathode gasket, 18 reverse Rather absorber, 18a: base material, 18b: reverse current absorbing layer, 19: bottom of anode chamber, 20: cathode chamber, 21: cathode, 22: metal elastic body, 23: current collector, 24: support, 30: partition, 40: Electrolytic Cathode Structure.
Explanation of the code | symbol about FIG. 108
10: electrode base for electrolysis, 20: first layer, 30: second layer, 100: electrode for electrolysis.
Explanation of the code | symbol about FIGS. 109-111
DESCRIPTION OF REFERENCE NUMERALS 1: ion exchange membrane, 2: carboxylic acid layer, 3: sulfonic acid layer, 4: reinforced core material, 10: membrane body, 11a, 11b: coating layer, 21, 22: reinforced core material, 100: electrolytic cell, 200: positive electrode, 300: negative electrode , 52: reinforcer, 504a: victim, 504: communication hole.
<Figure corresponding to the seventh embodiment>
Explanation of the code | symbol about FIGS. 112-118
Reference Signs List 1 electrolytic cell, 2 ion exchange membrane, 2a new ion exchange membrane, 4 electrolytic cell, 5 press machine, 6 negative electrode terminal, 7 anode terminal, 8 electrolytic cell frame, 9 laminate, 10 anode chamber, 11 12: anode gasket; 13: cathode gasket; 18: reverse current absorber; 18a: base material; 18b: reverse current absorbing layer; 19: bottom of anode chamber; 20: cathode chamber; 21: cathode; 22: metal elastic body 23: current collector, 24: support, 30: partition, 40: anode structure for electrolysis, 100: electrode for electrolysis.
Explanation of the code | symbol about FIG. 119
10: electrode base for electrolysis, 20: first layer, 30: second layer, 100: electrode for electrolysis.
Explanation of the code | symbol about FIGS. 120-122
DESCRIPTION OF REFERENCE NUMERALS 1: ion exchange membrane, 2: carboxylic acid layer, 3: sulfonic acid layer, 4: reinforced core material, 10: membrane body, 11a, 11b: coating layer, 21, 22: reinforced core material, 100: electrolytic cell, 200: positive electrode, 300: negative electrode , 52: reinforcer, 504a: victim, 504: communication hole.

Claims (60)

The electrolytic electrode whose mass per unit area is 48 mg / cm <2> or less, and the force applied per unit mass and unit area is 0.08 N / mg * cm <2> or more. The electrolytic electrode according to claim 1, wherein the electrolytic electrode includes an electrolytic electrode substrate and a catalyst layer, and the thickness of the electrolytic electrode substrate is 300 µm or less. The electrode for electrolysis according to claim 1 or 2, wherein a ratio measured by the following method (3) is 75% or more:
[Method (3)]
On both sides of the membrane of the perfluorocarbon polymer into which the ion exchanger was introduced, an ion exchange membrane (170 mm long) coated with inorganic particles and a binder and an electrode sample for electrolysis (130 mm long) were laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on a curved surface of a pipe of polyethylene (outer diameter of 145 mm) so that the electrode sample for electrolysis in the laminate is the outer side, and the laminate and the pipe are placed. A membrane in which inorganic particles and a binder are applied to both surfaces of the membrane of the perfluorocarbon polymer into which the ion exchanger is introduced, after being sufficiently immersed in pure water and removing the excess water adhering to the laminate surface and the pipe, The ratio (%) of the area of the part where the electrolytic electrode sample is in close contact is measured. The electrolytic electrode according to any one of claims 1 to 3, which has a porous structure and has a porosity of 5 to 90%. The electrolytic electrode according to any one of claims 1 to 4, which has a porous structure and has a porosity of 10 to 80%. The electrode for electrolysis in any one of Claims 1-5 whose thickness of the said electrode for electrolysis is 315 micrometers or less. The electrolytic electrode according to any one of claims 1 to 6, wherein the electrolytic electrode has a value measured by the following method (A) of 40 mm or less:
[Method (A)]
Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, a sample obtained by laminating an ion exchange membrane and the electrolytic electrode was wound and fixed on a curved surface of a vinyl chloride core material having an outer diameter of φ 32 mm, and left standing for 6 hours. Later, when the electrolytic electrode was separated and placed on a horizontal plate, the heights L ₁ and L ₂ in the vertical direction at both ends of the electrolytic electrode were measured, and these average values were measured. The electrolytic electrode according to any one of claims 1 to 7, wherein the electrolytic electrode has a size of 50 mm x 50 mm, a temperature of 24 ° C., a relative humidity of 32%, a piston speed of 0.2 cm / s, and an air flow rate of 0.4 cc /. The electrode for electrolysis whose ventilation resistance at the time of making it cm <2> / s is 24 kPa * s / m or less. The electrolytic electrode according to any one of claims 1 to 8, wherein the electrolytic electrode substrate contains at least one element selected from nickel (Ni) and titanium (Ti). The laminated body containing the electrode for electrolysis in any one of Claims 1-9. The winding body containing the electrode for electrolysis in any one of Claims 1-9, or the laminated body of Claim 10. An electrolytic electrode,
Diaphragm or feeder in contact with the electrolytic electrode
And
The laminated body whose force per unit mass and unit area of the said electrode for electrolysis with respect to the said diaphragm or feeder is less than 1.5 N / mg * cm <2>. The laminate according to claim 12, wherein a force applied per unit mass and unit area of the electrolytic electrode to the diaphragm or feeder is more than 0.005 N / mg · cm 2. The laminate according to claim 12 or 13, wherein the feed material is a wire mesh, a metal nonwoven fabric, a punching metal, an expanded metal or a foamed metal. The laminate according to any one of claims 12 to 14, having a layer comprising at least one surface layer of the diaphragm comprising a mixture of hydrophilic oxide particles and a polymer into which an ion exchanger is introduced. The laminate according to any one of claims 12 to 15, wherein a liquid is interposed between the electrolytic electrode and the diaphragm or the feeder. Diaphragm,
Electrolytic electrode fixed to at least one area of the surface of the diaphragm
Has,
The laminated body whose ratio of the said area | region in the surface of the said diaphragm is more than 0% and less than 93%. 18. The method of claim 17, wherein the electrode for electrolysis is Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag , Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , At least one catalyst component selected from the group consisting of Tb and Dy. The laminate according to claim 17 or 18, wherein at least part of the electrolytic electrode is fixed through the diaphragm in the region. The laminate according to any one of claims 17 to 19, wherein in the region, at least a part of the electrolytic electrode is located inside and fixed to the diaphragm. The laminate according to any one of claims 17 to 20, further comprising a fixing member for fixing the diaphragm and the electrolytic electrode. The laminate according to claim 21, wherein at least a part of the fixing member grips the diaphragm and the electrolytic electrode from the outside. The laminate according to claim 21 or 22, wherein at least a part of the fixing member magnetically fixes the diaphragm and the electrolytic electrode. The membrane according to any one of claims 17 to 23, wherein the diaphragm comprises an ion exchange membrane containing an organic resin in the surface layer,
The laminated body in which the said organic resin exists in the said area | region. The laminate according to any one of claims 17 to 24, wherein the diaphragm comprises a first ion exchange resin layer and a second ion exchange resin layer having an EW different from the first ion exchange resin layer. sieve. The laminate according to any one of claims 17 to 24, wherein the diaphragm comprises a first ion exchange resin layer and a second ion exchange resin layer having a functional group different from that of the first ion exchange resin layer. sieve. With the anode,
An anode frame supporting the anode;
An anode side gasket disposed on the anode frame;
A cathode facing the anode,
A cathode frame supporting the cathode;
A cathode side gasket disposed on the cathode frame and opposed to the anode side gasket;
A laminate comprising a diaphragm and an electrode for electrolysis, wherein the laminate is disposed between the anode side gasket and the cathode side gasket.
And
At least a part of the laminate is sandwiched between the anode side gasket and the cathode side gasket,
The air flow resistance is 24 kPa · s when the electrolytic electrode is 50 mm × 50 mm in size, having a temperature of 24 ° C., a relative humidity of 32%, a piston speed of 0.2 cm / s, and an air flow rate of 0.4 cc / cm 2 / s. Electrolyzer less than / m. The electrolytic cell according to claim 27, wherein the thickness of the electrode for electrolysis is 315 µm or less. The electrolytic cell according to claim 27 or 28, wherein the electrolytic electrode has a value measured by the following method (A) of 40 mm or less:
[Method (A)]
Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, a sample obtained by laminating an ion exchange membrane and the electrolytic electrode was wound and fixed on a curved surface of a vinyl chloride core material having an outer diameter of φ 32 mm, and left standing for 6 hours. Later, when the electrolytic electrode was separated and placed on a horizontal plate, the heights L ₁ and L ₂ in the vertical direction at both ends of the electrolytic electrode were measured, and these average values were measured. The electrolytic cell according to any one of claims 27 to 29, wherein a mass per unit area of the electrolytic electrode is 48 mg / cm 2 or less. The electrolytic cell according to any one of claims 27 to 30, wherein a force applied per unit mass and unit area of the electrolytic electrode is more than 0.005 N / mg · cm 2. The electrolyzer according to any one of claims 27 to 31, wherein the outermost periphery of the laminate is located outside the conduction surface direction than the outermost peripheries of the anode side gasket and the cathode side gasket. 33. The electrolytic electrode according to any one of claims 27 to 32, wherein Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y , Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd Electrolyzer comprising at least one catalyst component selected from the group consisting of Pm, Sm, Eu, Gd, Tb and Dy. The electrolyzer according to any one of claims 27 to 33, wherein at least a part of the electrode for electrolysis is fixed through the diaphragm in the laminate. The electrolytic cell according to any one of claims 27 to 33, wherein in the laminate, at least a part of the electrode for electrolysis is located inside and fixed to the diaphragm. The electrolytic cell according to any one of claims 27 to 35, further comprising a fixing member for fixing the diaphragm and the electrolytic electrode in the laminate. 37. The electrolytic cell according to claim 36, wherein at least part of said fixing member is fixed through said diaphragm and said electrolytic electrode in said laminate. 38. The electrolytic cell according to claim 36 or 37, wherein in said laminate, said fixing member comprises a soluble material that is soluble in an electrolyte solution. The electrolytic cell according to any one of claims 36 to 38, wherein in the laminate, at least a part of the fixing member grips the diaphragm and the electrolytic electrode from the outside. The electrolytic cell according to any one of claims 36 to 39, wherein in the laminate, at least a part of the fixing member fixes the diaphragm and the electrolytic electrode by magnetic force. 41. The membrane of any one of claims 27-40, wherein the diaphragm comprises an ion exchange membrane containing an organic resin in the surface layer,
An electrolytic cell in which the electrode for electrolysis is fixed in the organic resin. The electrolytic cell according to any one of claims 27 to 41, wherein the diaphragm comprises a first ion exchange resin layer and a second ion exchange resin layer having a different EW from the first ion exchange resin layer. . The manufacturing method of the electrolyzer as described in any one of Claims 27-42,
A method for producing an electrolytic cell, comprising the step of sandwiching the laminate between the anode side gasket and the cathode side gasket. As an update method of the laminated body in the electrolytic cell of any one of Claims 27-42,
Removing the laminate from the electrolytic cell by separating the laminate from the anode side gasket and the cathode side gasket;
Process of sandwiching the new laminate between the anode side gasket and the cathode side gasket
The update method of the laminated body which has this. A new electrolytic cell is disposed in an existing electrolytic cell having a positive electrode, a negative electrode facing the positive electrode, and a diaphragm disposed between the positive electrode and the negative electrode. As a method for producing
The manufacturing method of the electrolytic cell using the said electrode for electrolysis or the winding body of the said laminated body. The electrolytic cell manufacturing method of Claim 45 which has the process (A) which hold | maintains the said electrode for electrolysis or said laminated body in the wound state, and obtains the said wound body. The electrolytic cell manufacturing method of Claim 45 or 46 which has the process (B) of releasing the wound state of the said winding body. The manufacturing method of the electrolytic cell of Claim 47 which has a process (C) which arrange | positions the said electrode for electrolysis or the said laminated body on at least one surface of the said anode and the said cathode after the said process (B). As a method for updating an existing electrode by using an electrode for electrolysis,
The update method of the electrode using the winding body of the said electrode for electrolysis. The method of updating an electrode according to claim 49, further comprising a step (A ') of holding the electrolytic electrode in a wound state to obtain the wound body. The method of updating an electrode according to claim 49 or 50, further comprising a step (B ') of releasing the wound state of the electrolytic electrode. The method of updating an electrode according to claim 51, further comprising a step (C ') of disposing the electrolytic electrode on the surface of an existing electrode after the step (B'). A method for manufacturing a wound body for updating an existing electrolytic cell having a positive electrode, a negative electrode facing the positive electrode, and a diaphragm disposed between the positive electrode and the negative electrode,
The manufacturing method of the winding body which has a process of winding the laminated body of an electrode for electrolysis or the said electrode for electrolysis, and a new diaphragm, and obtaining the said wound body. A method for manufacturing a new electrolytic cell by disposing a laminate in an existing electrolytic cell having a positive electrode, a negative electrode facing the positive electrode, and a diaphragm disposed between the positive electrode and the negative electrode,
(A) obtaining the said laminated body by integrating an electrode for electrolysis and a new diaphragm under the temperature which the said diaphragm does not melt,
After the said process (A), the process (B) of exchanging the said diaphragm in an existing electrolytic cell with the said laminated body
Method for producing an electrolytic cell having a. 55. The method of claim 54, wherein said integration is performed under normal pressure. An electrolytic electrode and a new diaphragm are provided in an existing electrolytic cell having a positive electrode, a negative electrode facing the positive electrode, a diaphragm fixed between the positive electrode and the negative electrode, and an electrolytic cell frame supporting the positive electrode, the negative electrode and the diaphragm. As a method for producing a new electrolytic cell by disposing a laminate containing,
A step (A) of releasing the fixing of the diaphragm in the electrolytic cell frame,
After the said process (A), the process (B) of exchanging the said diaphragm and said laminated body
Method for producing an electrolytic cell having a. The electrolytic cell manufacturing method according to claim 56, wherein the step (A) is performed by sliding the positive electrode and the negative electrode in the arrangement direction thereof, respectively. The electrolytic cell manufacturing method according to claim 56 or 57, wherein after the step (B), the laminate is fixed in the electrolytic cell frame by pressing from the positive electrode and the negative electrode. The electrolytic cell according to any one of claims 56 to 58, wherein in the step (B), the laminate is fixed on at least one surface of the positive electrode and the negative electrode under a temperature at which the laminate does not melt. Way. Disposing an electrolytic electrode in an existing electrolytic cell having an anode, a cathode facing the anode, a diaphragm fixed between the anode and the cathode, and an electrolytic cell frame supporting the anode, the cathode and the diaphragm. As a method for producing new electrolytic cells,
A step (A) of releasing the fixing of the diaphragm in the electrolytic cell frame,
After the step (A), the step (B ') of disposing the electrolytic electrode between the diaphragm and the anode or the cathode.
Method for producing an electrolytic cell having a.

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