JPH0285387A - Sheetlike electrode material containing ion exchange resin, composite material thereof and production thereof - Google Patents

Abstract

PURPOSE:To obtain a sheetlike electrode material contg. ion exchange resin and having a three-dimensional electrochemically reactive surface and superior mechanical strength by adhering an ion exchange resin-contg. material to one side of a porous sheetlike substrate consisting of an F-contg. polymer as a binder and an electrochemically functional powdery material. CONSTITUTION:20-98wt.% electrochemically functional powdery material such as C powder, C powder supporting a Pt family metal or powder of a metal oxide such as RuO2, IrO2 or PbO2 is mixed with 2-80wt.% F-contg. polymer such as polytetrafluoroethylene as a binder and paste of the mixture is formed into a sheetlike body by rolling and heated to obtain a porous sheet having high porosity. A nonporous thin membrane is then formed on one side of the sheet with an ion exchange resin-contg. material, e.g., contg. a tetrafluoroethylenesulfonyl fluoride vinyl ether copolymer or further contg. <=50% metal such as Pt or Ir. A sheetlike electrode material contg. ion exchange resin and having superior performance in an electrochemical reaction is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sheet-like electrode material containing an ion exchange resin, a composite material thereof, and a manufacturing method thereof. More specifically, the present invention relates to a sheet-like electrode material containing an ion exchange resin having a three-dimensional electrochemical reaction surface and high mechanical strength, a composite material thereof, and a method for producing the same.

[Prior art and problems requiring solutions] Generally, the electrochemical reaction in an electrochemical cell occurs at the interface between the electrode and the electrolyte, and therefore the current/voltage characteristics of this electrochemical cell are dependent on the electrode and electrolyte. It is greatly influenced by the contact area with the electrolyte.

In particular, in the case of an electrolysis method using an ion exchange resin membrane as a solid electrolyte, there is a problem that the contact area between the electrode and the electrolyte is smaller than in the case of an aqueous solution electrolysis method.

JP-A No. 55-38934 discloses an ion exchange resin membrane and
One aspect of the disclosure discloses an electrode material comprising an electrode catalyst metal layer formed by an electroless plating method, but in this case, since the contact between the electrode and the electrolyte is two-dimensional (planar), It has been desired to further increase the contact area between the two.

JP-A-61-67786, 61-67788, 61
-67790 and 61-87887, etc.
For example, an electrode material is disclosed in which a resin layer containing an electrode catalyst powder and an ion exchange resin is combined on one or both sides of an ion exchange resin membrane based on a perfluorocarbon resin. However, in these electrode materials, the ion exchange resin powder is distributed throughout the electrode material, and the ion exchange resin is hydrophilic, making the entire electrode material hydrophilic, i.e., easily wetted by water. . When gas diffusion electrodes such as fuel cells and oxygen separation devices are constructed from such hydrophilic electrode materials, the electrode surface easily gets wet, which poses the problem of hindering gas supply to the device and reducing performance. arise.

In order to eliminate such inconvenience, Japanese Patent Application Laid-Open No. 616778
No. 7 and No. 61-67789 propose laminating a coating layer having a matrix of a hydrophobic resin, such as a perfluorocarbon resin, that does not contain an ion exchange resin on the outside of the electrode material containing an ion exchange resin. However, such electrode materials have complex structures and
It also has drawbacks such as being expensive.

Furthermore, in the above electrode material, since the ion exchange resin powder is dispersed in the electrode material, there is insufficient contact between the ion exchange resin powders, and therefore, the movement of hydrogen ions (H) in the electrode is inhibited. This results in a problem of low electrode effectiveness. In order to solve these problems, it is necessary to further increase the mixing ratio of the ion exchange resin powder, but this naturally results in the disadvantage that the hydrophilicity of the resulting electrode material becomes even higher. However, in some cases, the electrode catalyst may be coated with the ion exchange resin, resulting in inconveniences such as being unable to exhibit catalytic action.

JP 61-295387 and 61-295388
No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2003, discloses an electrode material consisting of an ion exchange resin membrane and a thin film layer of a mixture of an ion exchange resin and an electrode metal formed on one or both sides of the membrane. However, in these electrode materials, it is necessary to use an organic solvent or a mixed solvent of an organic solvent and water to form the thin film layer, and this solvent causes the ion exchange resin membrane to significantly swell. When this is dried, it shrinks violently, which causes the problem of cranking of the membrane.Also, considerable heat and pressure are required to firmly bond the ion exchange resin-metal mixture thin film to the ion exchange resin membrane. As a result, the resulting electrode material is crushed and becomes a substantially effective electrode.
This results in the disadvantage that the contact area at the electrolyte interface becomes considerably small.

Furthermore, the conventional electrode layer described above does not have self-retaining properties, or
Or, even if it has, it is extremely low, so in order to bond it to the ion exchange resin membrane, it is necessary to apply considerable heat and pressure, which often damages the ion exchange resin membrane and deteriorates the resulting electrode material. This has caused problems such as degrading the performance of the device or making it unusable.

Therefore, the present invention has a large effective contact area between the electrolyte and the electrode, and can be effectively used as a gas diffusion electrode.
Moreover, it can be easily manufactured without damaging the electrolyte membrane.
The present invention aims to provide a sheet-like electrode material containing an ion exchange resin, a composite thereof, and a method for manufacturing the same.

[Means and effects for solving the problem] The ion exchange resin-containing sheet electrode material of the present invention comprises a binder made of a fluorine-containing polymer and an electrochemically functional material powder dispersed therein. a sheet-like substrate comprising a large number of continuous pores, an ion exchange resin alone,
or an ion exchange resin-containing material made of a mixture of an ion exchange resin and a metal, and the ion exchange resin-containing material is continuously distributed within the continuous pores from one surface of the sheet-like substrate. It is characterized by this.

The sheet-like electrode material has a nonporous thin film formed of the ion-exchange resin-containing material on one surface of the sheet-like substrate, and a non-porous thin film formed of the ion-exchange resin-containing material on the other surface of the sheet-like substrate. The material may be substantially absent.

Furthermore, the above-mentioned sheet-like electrode material has a perfluorocarbon-containing ion-exchange resin membrane layer attached to one surface on which the ion-exchange resin-containing material is distributed, thereby forming an ion-exchange resin-containing sheet-like electrode/perfluorocarbon-containing sheet. An ion exchange resin membrane composite material may be formed.

The sheet-like substrate of the electrode material of the present invention is formed from a mixture of a binder made of a fluorine-containing polymer and electrochemically functional material powder dispersed and bonded therein.

Fluorine-containing polymer binders include, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA),
), tetrafluoroethylene-hexafluoroethylene copolymer (FEP), I-lifluorochloroethylene polymer (CPTFE), and tetrafluoroethylene-ethylene copolymer (ETFE), etc. Those made of seeds, particularly those made of PTFE, are preferred.

Electrochemically functional material powders include, for example, carbon powders such as graphite, carbon blank, and activated carbon powders, carbon powders supported with at least one metal having catalytic ability, such as platinum group metals, and catalysts. metal powder with functional properties (e.g. platinum black, palladium black, etc.)
, metal oxides (e.g. Ru0i, Ire, ,
Pb0z, etc.).

The blending ratio of the electrochemically functional material powder and the fluorine-containing polymer binder in the sheet-like substrate of the present invention varies depending on the use and desired characteristics of the electrode material to be produced, but in general, the electrochemically functional material powder The content of the fluorine-containing polymer binder is preferably 2 to 80 parts by weight relative to 20 to 98 parts by weight, and when the target electrode material is required to have high hydrophilicity, the content of the electrochemically functional material powder is When the desired Tj, t'N material is required to be hydrophobic, the content of the binder may be increased. If the binder content is less than 2 parts by weight based on 100 parts by weight of the binder-functional material mixture, the mechanical strength of the resulting sheet-like substrate will be insufficient, and if it is higher than 80 parts by weight, the resulting electrode material will be The electrochemical function of the electrochemical function becomes unsatisfactory.

-a, the sheet-like substrate used in the present invention has 50 to 40
Preferably it has a thickness of 0μ.

In the electrode material of the present invention, from an ion exchange resin alone,
Alternatively, an ion exchange resin-containing material made of a mixture of an ion exchange resin and a metal, particularly a metal having catalytic ability, is continuously distributed within the continuous pores from one surface of the sheet-like substrate.

The distribution amount of the ion exchange resin-containing material may have a gradient distribution from one side to the other side of the sheet-like substrate, for example, the distribution amount gradually decreases from one side to the other side. It may be distributed as follows.

The ion exchange resin used in the electrode material of the present invention functions as a solid electrolyte, and is, for example, a resin whose main chain is composed of a fluorine-containing hydrocarbon and has a cation exchange group bonded thereto, such as a tetrafluoride resin. It is preferable to use a copolymer of fluoroethylene and sulfonyl fluoride vinyl ether.

Furthermore, the metal in the solid electrolyte-containing material, particularly the metal having catalytic ability, is preferably made of at least one of platinum, iridium, palladium, rhodium, and the like. The metal content in the ion exchange resin-containing material is
Generally, it is 50% or less based on the weight of the ion exchange resin.

In the electrode material of the present invention, a nonporous thin film made of an ion exchange resin-containing material is formed on one side of a sheet-like substrate, and an ion-exchange resin-containing material is substantially formed on the other side of the sheet-like substrate. In other words, it is preferable that it not be present at all, or even if it is present, it should be in a very small amount.

The formation of such a non-porous ion exchange resin-containing material layer is
This is effective in improving the contact characteristics between the electrode material and the perfluorinated ion exchange resin as the solid electrolyte. Also,
The surface substantially free of the ion-exchange resin-containing material is effective as a gas supply path, a liquid permeation path, and as a cushion material between the ion-exchange resin-containing material membrane and the power supply (power supply). be.

The electrode material of the present invention may be made into an electrode composite material by laminating and bonding a perfluorohydrocarbon-containing ion-exchange resin membrane on one surface where the ion-exchange resin-containing material is distributed. Such composite materials reduce ohmic losses,
It also has the advantage of being easy to handle.

The method for producing the ion-exchange resin-containing sheet-like electrode material of the present invention is to produce a sheet-like substrate having a large number of continuous pores from a mixture containing a binder made of a fluorine-containing polymer and an electrochemically functional material powder. One side of this sheet-like substrate is brought into contact with an ion-exchange resin-containing solution, the solution is permeated into the sheet-like substrate from the one side, and the impregnated body is subjected to dry dust treatment, thereby , the ion exchange resin is continuously distributed and fixed in the continuous pores from one side of the sheet-like substrate.

Another method for producing the ion-exchange resin-containing sheet-like electrode material of the present invention is to use a mixture containing a binder made of a fluorine-containing polymer and an electrochemically functional material powder, which has a large number of continuous pores. forming a sheet-like substrate;
One side of this sheet-like substrate is brought into contact with a solution containing an ion exchange resin and a metal compound, the solution is impregnated into the sheet-like substrate from the one side, and the impregnated body is subjected to a drying treatment, and then , characterized in that the metal compound is subjected to a reduction treatment, whereby the mixture of the ion exchange resin and the metal is continuously distributed and fixed in the continuous pores from one side of the sheet-like substrate. It is.

In the method of the present invention, the sheet-like substrate can be produced by uniformly mixing a predetermined amount of electrochemically functional material powder and a fluorine-containing polymer binder, and then pressing this mixture. Alternatively, the above-mentioned mixture may be mixed with a liquid lubricant or not mixed, and may be rolled using heated rolls to form a sheet-like body. In the above sheet-like substrate manufacturing method, a large number of continuous pores are naturally formed between the electrochemically functional material powder particles in the sheet-like substrate.

The sheet-like substrate used in the present invention is
It may be manufactured by rolling or extruding a paste prepared by adding a liquid lubricant to a mixture of the electrochemically functional powder and a fluorine-containing polymer binder according to the method described in No. 979. Such a sheet-like substrate has high functional strength and allows easy control of porosity and pore diameter, and is therefore suitable for the method of the present invention.

When the ion exchange resin-containing material consists only of ion exchange resin, one side of the sheet-like substrate is brought into contact with a solution of at least one type of ion-exchange resin, and the solution is poured into the continuous pores of the sheet-like substrate. , permeate and impregnate from the contact surface, and dry the impregnated body thus obtained.Due to the impregnation process, the ion exchange resin solution continuously permeates and diffuses into the continuous pores from one surface of the sheet-like substrate. .At this time,
The distribution amount of the solution within the continuous pores may become smaller as the distance from the one surface increases. In other words, the amount of ion exchange resin solution impregnated into continuous pores is
The concentration may be distributed with a decreasing concentration gradient from one surface (surface in contact with the solution) to the other surface. If such an impregnated body is subjected to, for example, a drying treatment and, if necessary, a heat treatment, the solidified ion exchange resin is continuously distributed and fixed within the continuous pores from one side of the sheet-like substrate. At this time, the ion exchange resin may be distributed and fixed such that the distribution amount changes with a gradient from one surface to the other surface of the sheet-like substrate.

When the ion-exchange resin-containing material consists of an ion-exchange resin and a metal, particularly an electrode catalyst metal, a sheet-like substrate having a large number of continuous pores is prepared in the same manner as the above method, and one side of this sheet-like substrate is coated with at least one kind of pores. The substrate is brought into contact with a solution containing an ion exchange resin and at least one metal compound, and this solution is continuously impregnated into continuous pores from one side of the sheet-like substrate. Next, the impregnated body thus obtained is dried at a temperature of, for example, 50 to 90°C, and if necessary,
Heat treatment at a temperature of 10-170°C. Next, the dried metal compound in the ion exchange resin-metal compound mixture is subjected to a reduction treatment to reduce it to a metal. By these treatments, the ion exchange resin-containing material is continuously distributed and fixed in the continuous pores from one side of the sheet-like substrate. Of course, the distribution amount of the ion exchange resin-containing material within the continuous pores may be gradient from one surface to the other surface of the sheet-like substrate. In the method of the present invention, the ion exchange resin solution is prepared by dissolving the ion exchange resin in a solvent such as ethanol or a mixed solvent of ethanol and water. The concentration of the ion exchange resin in this solution is not particularly limited as long as the solution can penetrate into the sheet-like substrate, but it is generally used in the range of 0.5 to 20% by weight. The metal compound used in the method of the invention is one that is reducible to the corresponding metal and is selected from, for example, chloropentaamine platinum, chloropentanke modified palladium, and the like.

Generally, the metal compound is used so that the metal obtained by reduction accounts for 5 to 50% of the weight of the ion exchange resin. Hydrogen, sodium borohydride, hydrazine, etc. are used as the reducing agent for reducing the metal compound, and the reduction treatment is generally performed at a temperature of 15 to 180°C.

To penetrate and impregnate a sheet-like substrate with an ion-exchange resin solution or an ion-exchange resin-metal compound mixture solution, apply a predetermined amount of this solution to one surface of the sheet-like substrate and allow it to penetrate into continuous pores. Alternatively, the solution may be sucked up from one side of the sheet-like substrate into the continuous pores while applying vacuum suction treatment to the opposite side.

An ion exchange membrane may be bonded to the electrode material of the present invention, or the electrode material of the present invention may be bonded to a porous power supply material such as porous carbon or porous titanium, and this may be pressed against the ion exchange membrane. Alternatively, the electrode material of the present invention may be used simply by being pressed against the ion exchange membrane by means of a porous power supply. In order to join the above-mentioned membrane bodies to each other, at a temperature of 100 to 200°C, 1 to 200 kg/
It is necessary to perform heat-pressure welding at a pressure of cj.

In the method of the present invention, after the sheet-like substrate is adhered to a power supply or a current collector (for example, a porous carbon material or a titanium material), it may be subjected to an ion exchange resin impregnation treatment.

〔Example〕

The invention will be further illustrated by the following examples.

120 parts by weight of liquid lubricant (solvent naphtha) was added to a mixture of 35 parts by weight of carbon black carrying 10% by weight of platinum, 15 parts by weight of FEP powder, and 50 parts by weight of PTFE powder.
A paste was prepared by mixing parts by weight, and this paste was subjected to an extrusion and rolling process to form a sheet-like molded product with a thickness of 0.25 m.

This sheet-shaped molded product was heated to 200°C to achieve a porosity of 85%.
A porous sheet-like substrate was prepared.

An alcoholic solution of perfluorosulfonic acid resin having a concentration of 5% was diluted with ethanol to prepare a solution having a concentration of 3% by weight.

Applying the perfluorosulfonic acid resin solution at a coating amount of 20 d/rrr on one surface of the sheet-like substrate, and impregnating the solution from the solution-coated surface of the sheet-like substrate into the internal continuous pores thereof; The obtained impregnated body was dried at 120°C to prepare an electrode sheet.

The solution-applied surface of this electrode sheet exhibited a 90 degree contact angle with respect to water droplets. Therefore, even when wet with water and the electrode sheet surface was made vertical, the water wetting the surface did not flow down. . However, on the opposite side of the electrode sheet, water droplets moved freely in granular form, ie, this opposite side was not wetted by water. From this, it was confirmed that one side of this electrode sheet was covered with a thin layer of ion exchange resin, but no ion exchange resin oozed out on the opposite side.

The above electrode sheet is used as a cathode, and one side is plated with ion exchange resin (trademark: Nafion #117).
The platinum-plated surface of the ion-exchange resin thin layer of the electrode sheet was used as the anode, and the platinum-plated expanded titanium film was used as the current collector. The electrolytic device was assembled by pressing the current collector against the ion exchange resin membrane.

Pure water was supplied to the anode side of this electrolytic device, and air was supplied to the cathode side to construct an oxygen generating device. The current-voltage characteristics of this electrolyzer were measured, and the results are shown in FIG. In addition, in the above electrolytic apparatus, the electrode sheet and the ion exchange resin membrane were heated and pressurized at 170° C. and 6 kg/Cl1+ to join them together. The resulting electrolyzer exhibited properties similar to those described above.

On soil comparison, the same operation as in Example 1 was performed. However, instead of the electrode sheet described in Example 1, a sheet consisting of 40 parts by weight of platinum black powder and 60 parts by weight of PTFF was used.

The current-voltage characteristics of the obtained electrolyzer are shown in FIG.

Ground Comparison 1 The same operation as in Example 1 was performed. However, the sheet-like substrate was used as an electrode sheet without being subjected to ion exchange resin impregnation treatment.

The current-voltage characteristics of the obtained electrolyzer are shown in FIG.

Supporting evidence 1 The same operation as in Example 1 was performed. However, as an impregnating solution for the sheet-like substrate, an ion exchange resin with a concentration of 3 obtained by mixing an aqueous solution of chloropentaammine platinum (platinum concentration: 2 mg/d) with an alcohol solution of perfluorosulfonic acid resin (Nafion) Weight%, platinum concentration 0.5
A wt% solution was used. Further, after drying the impregnated body, it was subjected to hydrogen reduction treatment at a temperature of 150°C to reduce the platinum ammine complex to platinum.

The current-voltage characteristics of the obtained electrolyzer are shown in FIG.

Implementation ■1 Carbon blank 75 parts by weight, FEPl 0! A conductive material having a thickness of 1501 na and a porosity of 80% was prepared from a mixture of i parts by weight and 15 parts by weight of PTFE in the same manner as in Example 1.
A porous sheet-like substrate was created.

Separately, a mixed solution of 10 rILl of an ethanol solution containing 3% by weight of an ion exchange resin and 3 ml of an aqueous solution of chloropentaammonium platinum chloride containing 2% by weight of platinum was prepared.

This mixed solution was applied to one side of the sheet-like substrate in a coating amount of 20 a//d, and the other side was subjected to a vacuum treatment, and the mixed solution was sucked into the continuous pores of the sheet-like substrate to impregnate it. The solution was further applied to the coated surface of this impregnated body in a coating amount of 20ml to form a surface layer, and the impregnated body was heated to 50°C.
The platinum compound was reduced to platinum by drying it and heating it to a temperature of 120° C. in a hydrogen stream.

The obtained electrode sheet was used as a cathode, and the thickness was 200 mm.
Current ion exchange resin membrane (trademark: Nafion #117,
(manufactured by DuPont), and an electrolytic device was assembled using, as an anode, the above-mentioned ion exchange resin membrane plated with platinum at 4 cm/c1i by an electroless plating method.

Water electrolysis was performed using this electrolyzer. The current-voltage characteristics of this electrolyzer are shown in FIG.

le twist master Ion exchange resin membrane (trademark: Nafion #117).

Water electrolysis was carried out in the same manner as in Example 3 using an electrolytic device obtained by applying platinum plating of 4 μm/cd using an electroless plating method on both sides of a 200μ1 m thick (manufactured by DuPont). The current-voltage characteristics of this electrolyzer are shown in FIG.

Lead dioxide (PbO□, average particle size; 5j1
1a) 95 parts by weight, 1 part by weight of FEP and PTl'E
A co-agglomerated mixture consisting of 4 parts by weight was prepared and subjected to extrusion and roll rolling to produce a 50-thick pbo□-containing porous sheet-like substrate.

5% by weight of ion exchange resin on one side of the sheet-like substrate.
A solution (solvent: ethanol) was applied at a coating amount of 20aj/r4 and treated in the same manner as in Example 1 to prepare an electrode sheet.

This electrode sheet was laminated with the solution coated side facing the ion exchange resin membrane (trademark: Nafion #117), and
0℃, 70kg/a! The two were bonded together by heating and pressurizing to form a composite A.

A co-agglomerated mixture consisting of 35 parts by weight of carbon black carrying 10% by weight of platinum, 45 parts by weight of FEP 2 (Nll) and PTFE was prepared by a complex co-agglomeration method.
A porous sheet-like substrate having a thickness of 130 mm was prepared from this mixture by a roll rolling method.

This sheet-like substrate was bonded to a multilayer SUS mesh (surface N: 65 mesh) whose surface had been treated with fluororesin by heating and pressing at 350° C. and 1 kg/cd. The same ion exchange resin-chloropentaammine platinum mixed solution as described in the example was applied to the surface of the sheet-like substrate of this bonded body at a coating amount of 20-/I, and the S of the bonded body was
The mixed solution was suctioned and impregnated into the continuous pores of the sheet-like substrate by suctioning under reduced pressure from the US Me/Noche side. Furthermore, the mixed solution was applied to the surface of the sheet-like substrate at a coating amount of 20 nu/m,
This impregnated bonded body was dried at 50°C and subjected to hydrogen reduction treatment at 120°C to precipitate platinum. Complex B was obtained.

1. Apparatus 1. Sole construction An electrolytic device was assembled using the PbO2-containing electrode sheet of composite A as an anode and the electrode sheet of composite B as a cathode.

Pure water was supplied to the anode side of this electrolyzer, and air was supplied to the cathode side to perform electrolysis.

The t current-voltage characteristics at this time are shown in FIG. Furthermore, although oxygen containing ozone at a concentration of approximately 13% was obtained from the anode side by the above electrolytic operation, no hydrogen generation was observed on the quad side.

Comparative Example 2 The same operation as in Example 4 was carried out. However, in composites A and B, impregnation with the ion exchange resin-containing solution was not performed.

The current-voltage characteristics of the obtained electrolyzer are shown in FIG.

Carbon black 40 supports 10% by weight of platinum using the 1 fan co-aggregation method! ! Parts by weight, 20 parts by weight of FEP and PTF
A co-agglomerated mixture consisting of 40 parts by weight of E was prepared, precipitated and rolled to a thickness of 200 I! A porous sheet-like substrate of m was prepared.

This sheet-like substrate was bonded to carbon paper whose surface had been water-repellent treated with a fluororesin by heating and pressing at 355° C. and 1 kg/cd.

- The same ion exchange resin-chloropentaammine platinum mixed solution as described in Example 2 was applied to the surface of the sheet-like substrate of the composite thus obtained at a coating amount of 20 tal/cd, and the composite was The mixed solution was suctioned and impregnated into the continuous pores of the sheet-like substrate by suctioning under reduced pressure from the carbon paper side. The impregnated composite was dried at 50°C, and
Hydrogen reduction was performed at 120° C. to precipitate platinum to prepare a composite electrode sheet.

Two composite electric bridge sheets are laminated with the carbon paper placed on the outside, and an ion exchange resin membrane (
Trademark: Nafion #117, 20On)
The three components were heated and pressurized at 170° C. and 3 kg/cd to integrate them.

Humidified hydrogen gas was supplied to one side of the electrolyzer thus obtained, and air was supplied to the other side to construct an SPE type fuel cell, which was operated. The current-voltage characteristics at this time are shown in FIG.

〔Effect of the invention〕

The electrode material of the present invention has the following characteristics.

1. Since the ion exchange resin is continuously distributed and fixed in the continuous pores of the sheet-like substrate, a continuous contact surface between the electrode and the electrolyte is formed three-dimensionally, and therefore hydrogen ions (H'') ) moves smoothly, so the electrochemical reaction is carried out efficiently.

2. The amount and distribution of the ion exchange resin impregnated into the sheet-like substrate can be set and manufactured as desired.

3. By making one side of the electrode material hydrophobic without the presence of ion exchange resin, this can be used for applications such as fuel cells 1 and gas diffusion electrodes for oxygen separation devices.

4. One side of the electrode material is coated with an ion exchange resin layer,
It has increased hydrophilicity and can be used for applications such as water electrolysis, salt electrolysis, and hydrochloric acid electrolysis.

5. By using a high-strength membrane body (for example, one made by the method described in Japanese Patent Publication No. 19979/1983) as the sheet-like substrate, it is possible to simply attach it closely to the ion exchange resin membrane or power supply without bonding it. Sufficient self-supporting properties can be obtained.

6. There is no need to form electrodes on the ion exchange membrane, so there is no damage to the electrode material.

7. Even when the ion exchange membrane is heated and pressed, there is almost no reduction in the three-dimensional reaction interface area within the electrode material.

8. Since a three-dimensional reaction interface is formed in the conductive sheet-like substrate, the efficiency of power supply (for example, in oxygen separation devices and water electrolysis devices) and current collection (for example, in fuel cells) is extremely high. This effect is particularly enhanced by distributing the mixture of ion exchange resin and metal into the continuous pores of the sheet-like substrate.

9. Since the sheet-like substrate is not swollen by a solvent, the step of impregnating it with an ion-exchange resin-containing solution is easy, and a high-performance electrode material can be obtained efficiently.

[Brief explanation of the drawing]

FIG. 1, FIG. 2, FIG. 3, and FIG. 4 are graphs showing the current-voltage characteristics of an electrolytic device obtained using the sheet-like electrode material of the present invention and a comparative electrolytic device, respectively. Figure 1 Figure 2

Claims (1)

[Scope of Claims] 1. A sheet-like substrate comprising a binder made of a fluorine-containing polymer and electrochemically functional material powder dispersed therein, and having a large number of continuous pores; an ion-exchange resin-containing material consisting of an ion-exchange resin alone or a mixture of an ion-exchange resin and a metal, and the ion-exchange resin-containing material is continuous from one side of the sheet-like substrate into the continuous pores. A sheet-like electrode material containing ion exchange resin, which is distributed as follows. 2. The sheet-like electrode material according to claim 1, wherein the ion-exchange resin-containing material forms a nonporous thin film on one surface of the sheet-like substrate and is substantially absent on the other surface. 3. It consists of the ion exchange resin-containing sheet-like electrode material according to claim 1 or 2, and a perfluorohydrocarbon-containing ion-exchange resin membrane layer, and this membrane layer is made of the ion-exchange resin-containing material of the sheet-like electrode material. A sheet-like electrode composite material containing an ion-exchange resin, which is bonded to one surface where the ion-exchange resin is distributed. 4. A sheet-like substrate having a large number of continuous pores is formed from a mixture containing a binder made of a fluorine-containing polymer and an electrochemically functional material powder, and one side of this sheet-like substrate is coated with an ion-exchange resin-containing solution. The solution is infiltrated into the continuous pores of the sheet-like substrate from the one side, and the impregnated body is subjected to a drying treatment, whereby the ion-exchange resin is applied from one side of the sheet-like substrate to the continuous pores of the sheet-like substrate. A method for producing a sheet-like electrode material containing an ion exchange resin, comprising distributing it continuously in pores. 5. A sheet-like substrate having a large number of continuous pores is formed from a mixture containing a binder made of a fluorine-containing polymer and an electrochemically functional material powder, and one side of this sheet-like substrate is covered with an ion exchange resin and a metal. contact with a solution containing the metal compound to infiltrate the continuous pores of the sheet-like substrate from the one surface, drying the impregnated body, and further reducing the metal compound; The mixture of the ion exchange resin and metal is
A method for producing a sheet-like electrode material containing an ion-exchange resin, comprising distributing it continuously into the continuous pores from one side of the sheet-like substrate.