JP2770958B2 - Sheet electrode material containing ion-exchange resin, composite material thereof and method for producing the same - Google Patents

Description

The present invention relates to an ion-exchange resin-containing sheet electrode material, a composite material thereof, and a method for producing the same.
More specifically, the present invention relates to an ion exchange resin-containing sheet electrode material having a three-dimensional electrochemical reaction surface and high mechanical strength, a composite material thereof, and a method for producing the same.

[Conventional technologies and issues requiring solutions]

Generally, an electrochemical reaction in an electrochemical cell occurs at an interface between an electrode and an electrolyte. Therefore, current / voltage characteristics of the electrochemical cell largely depend on a contact area between the electrode and the electrolyte. In particular, in the case of the electrolysis method using the ion exchange resin membrane as the solid electrolyte, there is a problem that the contact area between the electrode and the electrolyte is smaller than in the case of the aqueous solution electrolysis method.

JP-A-55-38934 discloses an electrode material comprising an ion-exchange resin membrane and, on one side thereof, an electrode catalyst metal layer formed by an electroless plating method.
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, for example, include, for example, an electrode catalyst powder and an ion-exchange resin on one or both surfaces of an ion-exchange resin membrane based on a perfluorocarbon resin. An electrode material in which a resin layer containing an exchange resin is combined is disclosed. However,
In these electrode materials, the ion exchange resin powder is
Since the ion exchange resin is distributed throughout the electrode material and the ion exchange resin is hydrophilic, the entire electrode material is hydrophilic, that is, easily wet with water. When a gas diffusion electrode such as a fuel cell and an oxygen separation device is formed from such a hydrophilic electrode material, the electrode surface is easily wetted, which hinders gas supply to the device and lowers performance. Occurs.

To solve such inconveniences, Japanese Patent Application Laid-Open No. 61-67787
No., 61-67789, and the like, it is proposed to laminate a coating layer having a matrix of a hydrophobic resin not containing an ion exchange resin, for example, a perfluorocarbon resin, on the outside of the ion exchange resin-containing electrode material. But,
Such an electrode material has drawbacks such as a complicated structure and high cost.

Furthermore, in the above-mentioned electrode material, since the ion-exchange resin powder is dispersed in the electrode material, the contact between the ion-exchange resin powders is not sufficient, and therefore, the movement of hydrogen ions (H ⁺ ) in the electrode is reduced. Insufficiency results in a problem that the effect of the electrode is low. In order to solve such a problem, it is necessary to further increase the mixing ratio of the ion-exchange resin powder. However, in this case, there is a disadvantage that the hydrophilicity of the obtained electrode material is naturally further increased. In some cases, the electrode catalyst may be covered with the ion exchange resin, and may not be able to exhibit a catalytic action.

JP-A-61-295387 and JP-A-61-295388 disclose an electrode material comprising 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 surfaces thereof. ing. However, in these electrode materials, it is necessary to use an organic solvent or a mixed solvent of an organic solvent and water for forming the thin film layer, and the ion exchange resin membrane is significantly swollen by this solvent, When this is dried, it shrinks violently, so there is a disadvantage that cracks occur in this membrane.
Strong bonding of the ion-exchange resin-metal mixture thin film requires considerable heating and pressurization, which crushes the resulting electrode material and results in a substantially smaller effective electrode-electrolyte interface contact area. Inconvenience that it becomes.

Furthermore, since the above-mentioned conventional electrode layer does not have self-holding property or has very low self-holding property, it is necessary to apply considerable heat and pressure to join it to the ion exchange resin membrane. For this reason, the ion exchange resin membrane is often damaged, causing problems such as lowering the performance of the obtained electrode material or making it unusable.

Therefore, the present invention provides an ion-exchange resin-containing sheet which has a large effective contact area between the electrolyte and the electrode, can be effectively used as a gas diffusion electrode, and can be easily manufactured without damaging the electrolyte membrane. An object is to provide an electrode material, a composite thereof, and a manufacturing method thereof.

[Means for solving the problem and operation]

According to the present invention, a binder comprising a fluorine-containing polymer, comprising a carbon powder dispersed therein, and a sheet-like substrate having a large number of continuous pores, ion-exchange resin alone, or, An ion-exchange resin-containing material comprising a mixture of an ion-exchange resin and a metal, wherein the ion-exchange resin-containing material is continuously formed in the continuous pores from one surface of the sheet-like substrate in the entire thickness direction. An ion-exchange resin-containing sheet electrode material is provided having a concentration gradient that is distributed and decreases from one surface to the other.

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

Further, the above-mentioned sheet-like electrode material is obtained by binding a perfluorocarbon-containing ion-exchange resin membrane layer on one surface on which the ion-exchange resin-containing material is distributed, and forming the ion-exchange resin-containing sheet electrode / perfluorocarbon-containing electrode. An ion exchange resin membrane composite material may be formed.

The sheet-shaped substrate of the electrode material of the present invention is formed from a mixture of a binder made of a fluorine-containing polymer and carbon powder that is an electrochemically functional material dispersed and bound therein. is there.

Examples of the fluorine-containing polymer binder include polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoroethylene copolymer (FEP), and trifluorochloroethylene polymer. (CPTF
E) and at least one selected from tetrafluoroethylene-ethylene copolymer (ETFE) and the like, particularly preferably PTFE.

Carbon powder, such as graphite, carbon black,
And activated carbon powders, and those containing at least one platinum group metal supported on these carbon powders.

The mixing ratio of the carbon powder, which is an electrochemically functional material, 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. 20 to 98 parts by weight of the powder, preferably 2 to 80 parts by weight of the fluorine-containing polymer binder, and when the target electrode material is required to have high hydrophilicity, increase the content of the carbon powder, When the target electrode material is required to be hydrophobic, the content of the binder may be increased. When the binder content is less than 2 parts by weight based on 100 parts by weight of the binder-carbon powder mixture, the mechanical strength of the obtained sheet-like substrate is insufficient, and when it is higher than 80 parts by weight, the obtained electrode material is Will have unsatisfactory electrochemical function. Generally, the sheet-like substrate used in the present invention preferably has a thickness of 50 to 400 μm.

In the electrode material of the present invention, an ion-exchange resin alone or an ion-exchange resin-containing material composed of a mixture of an ion-exchange resin and a metal, particularly a metal having a catalytic ability, is continuously formed in continuous pores from one surface of the sheet-like substrate. Are distributed. The distribution amount of the ion-exchange resin-containing material may have a gradient distribution from one surface to the other surface of the sheet-like substrate.For example, the distribution amount gradually decreases from one surface side to the other surface 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. For example, a resin in which a fluorine-containing hydrocarbon is a main component of a main chain and a cation exchange group is bonded to the main component, for example, It is preferable to use a copolymer of fluoroethylene and sulfonyl fluoride vinyl ether.

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

In the electrode material of the present invention, a nonporous thin film formed from an ion-exchange resin-containing material is formed on one surface of a sheet-like substrate, and the ion-exchange resin-containing material is substantially formed on another surface of the sheet-like substrate. It is preferred that they are not present in all cases, that is, that they are not present at all or that they are present in very small amounts.

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

The electrode material of the present invention may be formed as an electrode composite material by laminating and binding a perfluorohydrocarbon-containing ion-exchange resin membrane on one surface where the ion-exchange resin-containing material is distributed. Such a composite material has advantages such as reduced ohmic loss and improved handleability.

The method for producing a sheet-like electrode material containing an ion-exchange resin of the present invention comprises forming a sheet-like substrate having a large number of continuous pores from a mixture containing a binder comprising a fluorine-containing polymer and carbon powder, One surface of the sheet-like substrate is brought into contact with a solution containing an ion-exchange resin, and the solution is impregnated and impregnated from the one surface into the sheet-like substrate, and the impregnated body is subjected to a drying treatment. And distributing and fixing continuously from one surface of the sheet-like substrate into the continuous pores.

Another method for producing the sheet electrode material containing the ion exchange resin of the present invention is to form a sheet substrate having a large number of continuous pores from a mixture containing a binder comprising a fluorine-containing polymer and carbon powder. Then, one surface of the sheet substrate is brought into contact with a solution containing an ion-exchange resin and a metal compound, the solution is impregnated from the one surface into the sheet substrate, and the impregnated body is subjected to a drying treatment. ,
Further, 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 surface of the sheet-shaped substrate. Things.

In the method of the present invention, the sheet-like substrate can be produced by uniformly mixing a predetermined amount of carbon powder and a fluorine-containing polymer binder, and hot-pressing this mixture. Alternatively, the above mixture may be mixed with a liquid lubricant or may be rolled with a heating roll without mixing to form a sheet. In the above-mentioned sheet-like substrate manufacturing method, many continuous pores are naturally formed between the carbon powder particles in the sheet-like substrate.

The sheet-like substrate used in the present invention is described in JP-B-63-1997.
According to the method described in No. 9, a paste prepared by adding a liquid lubricant to a mixture of the carbon powder and the fluorine-containing polymer binder is stretched as necessary after rolling or extruding, or the stretched material is further compressed. May be manufactured. Such a sheet-like substrate has high functional strength, and porosity and pore diameter can be easily controlled,
Therefore, it is suitable for the method of the present invention.

When the ion-exchange resin-containing material is composed of only the ion-exchange resin, one surface of the sheet-like substrate is brought into contact with a solution of at least one ion-exchange resin, and the solution is placed in continuous pores of the sheet-like substrate. Impregnation and impregnation are performed from the contact surface, and the impregnated body thus obtained is dried. Due to the impregnation treatment, the ion exchange resin solution continuously permeates and diffuses from one surface of the sheet-like substrate into the continuous pores. At this time, the distribution amount of the solution in the continuous pores may decrease as the distance from the one surface increases. In other words, the continuous pore impregnation amount of the ion exchange resin solution may be distributed with a decreasing concentration gradient from one surface (the surface in contact with the solution) to the other surface of the sheet-like substrate. If such an impregnated body is subjected to, for example, a drying treatment and, if necessary, a further heat treatment, the solidified ion-exchange resin is continuously distributed and fixed from one surface of the sheet-like substrate into the continuous pores. At this time, the ion exchange resin may be distributed and fixed so that the distribution amount changes from one surface of the sheet-shaped substrate to the other surface with a gradient.

The ion exchange resin containing material is made of an ion exchange resin and a metal,
Particularly when the electrode catalyst metal is used, a sheet-like substrate having a large number of continuous pores is prepared in the same manner as the above method, and one surface of the sheet-like substrate is at least one type of ion exchange resin.
Contacting a solution containing at least one metal compound;
This solution is continuously infiltrated and impregnated from one surface of the sheet-like substrate into continuous pores. 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 ~ 170 ° C. Next, the dried metal compound in the ion-exchange resin-metal compound mixture is subjected to a reduction treatment to reduce the metal compound to a metal. By these treatments, the ion exchange resin-containing material is continuously distributed and fixed from one surface of the sheet-like substrate into the continuous pores. Of course, the distribution amount of the ion-exchange resin-containing material in the continuous pores may have a gradient from one surface of the sheet-like substrate to the other surface. In the method of the present invention, the ion exchange resin solution is prepared by dissolving the ion exchange resin in a solution 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 this solution can penetrate into the sheet-like substrate, but is generally used in the range of 0.5 to 20% by weight. The metal compound used in the method of the present invention can be reduced to a corresponding metal and is selected from, for example, chloropentaammineplatinum and chloropentaneamminepalladium.

Generally, the metal compound is used so that the metal obtained by reduction is 5 to 50% based on the weight of the ion exchange resin. For the reduction of the metal compound, hydrogen, sodium borohydride, hydrazine, or the like is used as a reducing agent, and the reduction treatment is generally performed at a temperature of 15 to 180 ° C. To permeate and impregnate the sheet-like substrate with the ion-exchange resin solution or the ion-exchange resin-metal compound mixture solution, a predetermined amount of this solution is applied to one surface of the sheet-like substrate, and is allowed to penetrate into continuous pores. Alternatively, the solution may be sucked into the continuous pores from one surface of the sheet-like substrate while performing the vacuum suction treatment on the opposite surface side.

An ion exchange membrane may be bonded to the electrode material of the present invention,
Alternatively, the electrode material of the present invention may be bonded to a porous power feeder such as porous carbon or porous titanium and pressed against an ion exchange membrane for use. Alternatively, the electrode material of the present invention may be used. Alternatively, it may be used simply by pressing against the ion exchange membrane with a porous power supply. In order to bond the above-mentioned film bodies to each other, it is necessary to heat-press at a temperature of 100 to 200 ° C. and a pressure of 1 to 200 kg / cm ² .

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

〔Example〕

 The present invention is further described by the following examples.

Example 1 A paste was prepared by mixing 120 parts by weight of a liquid lubricant (solvent naphtha) with a mixture of 35 parts by weight of carbon black supporting 10% by weight of platinum, 15 parts by weight of FEP powder, and 50 parts by weight of PTFE powder. This paste was subjected to an extrusion and rolling process to obtain a 0.25 mm thick sheet-like molded product.

This sheet-like molded product was heated to 200 ° C. to prepare a porous sheet-like substrate having a porosity of 85%.

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

On one surface of the sheet substrate, the perfluorosulfonic acid resin solution was coated at a coverage of 20 ml / m ^2, the solution from the solution coated surface of the sheet substrate, impregnated impregnated therein continuous pores, The obtained impregnated body is dried at 120 ° C,
An electrode sheet was prepared. The solution-coated side surface of the electrode sheet showed a contact angle of 90 degrees with respect to water droplets, and therefore, even when wet with water and the electrode sheet surface was vertical, the water that wet the surface did not flow down. . However, on the opposite side of the electrode sheet, water droplets were free to move in a granular manner, that is, the opposite side was not wet by water. From this, it was confirmed that one surface of the electrode sheet was covered with the ion exchange resin thin layer, but the ion exchange resin did not exude on the opposite surface.

The electrode sheet was used as a cathode, and the platinum-plated surface of an ion-exchange resin membrane (trademark: Nafion # 117, manufactured by DuPont, 0.2 mm in thickness) with one surface plated with platinum was used as an anode, and further platinum-plated. Using an expanded titanium film as a current collector, an electrolysis apparatus was assembled by pressing the thin layer surface of the ion exchange resin of the electrode sheet toward the ion exchange resin film with the current collector.

Pure water was supplied to the anode side of this electrolysis apparatus, and air was supplied to the cathode side to form an oxygen generator. The current-voltage characteristics of this electrolytic device were measured, and the results are shown in FIG. Further, in the electrolysis apparatus, the electrode sheet and the ion exchange resin membrane, 170 ° C., subjected to heating and pressure of 6 kg / cm ² ,
These were joined. The obtained electrolysis device showed the same characteristics as those described above.

Comparative Example 1 The same operation as in Example 1 was performed. However, a sheet composed of 40 parts by weight of platinum black powder and 60 parts by weight of PTFE was used instead of the electrode sheet described in Example 1.

 FIG. 1 shows the current-voltage characteristics of the obtained electrolytic device.

Comparative Example 2 The same operation as in Example 1 was performed. However, the sheet-like substrate was used as an electrode sheet without subjecting it to an ion exchange resin impregnation treatment.

 FIG. 1 shows the current-voltage characteristics of the obtained electrolytic device.

Example 2 The same operation as in Example 1 was performed. However, as an impregnating solution for the sheet-like substrate, an aqueous solution of chloropentaammineplatinum (platinum concentration: 2 mg / ml) was mixed with an alcohol solution of perfluorosulfonic acid resin (Nafion), and the ion exchange resin concentration was 3% by weight. %, A solution having a platinum concentration of 0.5% by weight was used. After drying the impregnated body,
A hydrogen reduction treatment was performed at a temperature of 0 ° C. to reduce the platinum ammine complex to platinum.

 FIG. 1 shows the current-voltage characteristics of the obtained electrolytic device.

Example 3 75 parts by weight of carbon black, 10 parts by weight of FEP and PTFE1
From 5 parts by weight of the mixture, a thickness of 1 was obtained by the same operation as in Example 1.
A conductive and porous sheet-like substrate having a thickness of 50 μm and a porosity of 80% was prepared.

Separately, a mixed solution of 10 ml of an ethanol solution containing 3% by weight of 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 surface of the sheet-like substrate at a coating amount of 20 ml / m ² , and the opposite surface was subjected to a reduced pressure treatment, and the mixed solution was sucked and impregnated into the continuous pores of the sheet-like substrate. The further the solution to the coated surface of the impregnated material was applied at a coverage of 20 ml / m ^2, to form a surface layer, the impregnated material was dried at 50 ° C.,
The platinum compound was reduced to platinum by heating to a temperature of 120 ° C. in a stream of hydrogen.

The obtained electrode sheet was used as a cathode, and this was
A 4 μm / cm ² platinum-plated ion-exchange resin membrane was used as the anode by electroless plating. The device was assembled.

Water electrolysis was performed using this electrolysis apparatus. FIG. 2 shows the current-voltage characteristics of this electrolytic device.

Comparative Example 3 On both surfaces of an ion-exchange resin membrane (trade name: Nafion # 117, manufactured by DuPont, 200 μm thick), 4
Water electrolysis similar to that of Example 3 was performed using an electrolysis apparatus obtained by performing platinum plating of mg / cm ² . FIG. 2 shows the current-voltage characteristics of this electrolytic device.

Example 4 Preparation of Composite A Lead dioxide (PbO ₂ , average particle size: 5 μm) 95 by a co-aggregation method
Parts by weight, 1 part by weight of FEP and 4 parts by weight of PTFE were prepared, extruded and roll-rolled to a thickness of
A 50 μm PbO ₂ -containing porous sheet-like substrate was prepared.

A 5% by weight solution of an ion exchange resin (solvent: ethanol) was applied to one surface of the sheet-like substrate at a coating amount of 20 ml / m ² , and processed in the same manner as in Example 1 to prepare an electrode sheet.

The electrode sheet is laminated with its solution-coated surface facing an ion-exchange resin membrane (trademark: Nafion # 117),
The two were joined by heating and pressing at 70 ° C. and 70 kg / cm ² to obtain a composite A.

Preparation of Composite B A co-agglomeration mixture consisting of 35 parts by weight of carbon black supporting 10% by weight of platinum, 20 parts by weight of FEP and 45 parts by weight of PTFE was prepared by a co-aggregation method, and the mixture was roll-thickened from this mixture. A porous sheet-like substrate having a thickness of 130 μm was prepared.

This sheet-shaped substrate is coated with a 350 SUS mesh (surface layer: 65 mesh) which has been subjected to a water-repellent treatment with a fluororesin.
Bonding was performed by heating and pressing at 1 ° C. and 1 kg / cm ² . The same ion exchange resin-chloropentaammineplatinum mixed solution as described in the examples was applied to the sheet-like substrate surface of this bonded body.
The mixture was applied at an application amount of 20 ml / m ² , and the mixture was suctioned under reduced pressure from the SUS mesh side of the joined body. Further, the mixed solution is applied to the surface of the sheet-like substrate.
The impregnated joined body was dried at 50 ° C., and subjected to a hydrogen reduction treatment at 120 ° C. to deposit platinum at a coating amount of 20 ml / m ² . Complex B was obtained.

Preparation of Electrolytic Device An electrolytic device was assembled using the PbO ₂ -containing electrode sheet of the composite A as an anode and the electrode sheet of the composite B as a cathode.

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

FIG. 3 shows the current-voltage characteristics at this time. Further, oxygen containing about 13% concentration of ozone was obtained from the anode side by the above electrolysis operation, but no generation of hydrogen was observed on the cathode side.

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

 FIG. 3 shows current-voltage characteristics of the obtained electrolytic device.

Example 5 A co-agglomeration mixture consisting of 40% by weight of carbon black supporting 10% by weight of platinum, 20 parts by weight of FEP, and 40 parts by weight of PTFE was prepared by a co-aggregation method, and the mixture was deposited and rolled to obtain a 200 μm-thick porous film. A porous sheet-like substrate was prepared.

This sheet-shaped substrate was bonded to carbon paper that had been subjected to a water-repellent treatment with a fluororesin by heating and pressing at 355 ° C. and 1 kg / cm ² .

ml The same ion-exchange resin-chloropentaammineplatinum mixed solution as described in Example 2 was applied to the sheet-like substrate surface of the composite thus obtained at a coating amount of 20 ml / m ² to obtain the composite. Vacuum suction from the carbon paper side of
The mixed solution was suction-impregnated into the continuous pores of the sheet-like substrate.
The impregnated composite was dried at 50 ° C., and subjected to hydrogen reduction at 120 ° C. to precipitate platinum to prepare a composite electrode sheet.

The two composite electrode sheets are laminated so that the carbon paper is disposed on the outside, and an ion exchange resin (trademark: Nafion # 117,200 μm) is inserted between both layers. The pieces were integrated by heating and pressing at cm ² .

A humidified hydrogen gas was supplied to one side of the electrolysis apparatus and air was supplied to the other side of the electrolysis apparatus thus obtained, and an SPE type fuel cell was constructed and operated. FIG. 4 shows the current-voltage characteristics at this time.

〔The invention's effect〕

 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 thus hydrogen ions (H ⁺ ) Since the movement of the particles proceeds smoothly, the electrochemical reaction is efficiently performed.

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

3. One surface of the electrode material can be made hydrophobic without an ion-exchange resin, and used for gas diffusion electrodes such as fuel cells and oxygen separators.

4. One side of electrode material is covered with ion exchange resin layer,
The hydrophilicity is enhanced, and this can be used for applications such as water electrolysis, salt electrolysis, and hydrochloric acid electrolysis.

5. A high-strength film (eg, JP-B-63
Using the method of No. 19979), a sufficient self-supporting property can be obtained simply by adhering to the ion-exchange resin membrane or the power feeder without joining.

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

7. Even when heated and pressed against the ion exchange membrane, the three-dimensional reaction interface area in the electrode material hardly decreases.

8. Since a three-dimensional reaction interface is formed in the conductive sheet-like substrate, power supply (eg, in an oxygen separator, a water electrolyzer) and power collection (eg, in a fuel cell) efficiency are extremely high. This effect is particularly enhanced by distributing the mixture of the ion exchange resin and the metal in the continuous pores of the sheet-like substrate.

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

[Brief description of the drawings]

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

Claims (5)

(57) [Claims] 1. A binder comprising a fluorine-containing polymer,
A sheet-like substrate comprising carbon powder dispersed therein and having a large number of continuous pores; and an ion-exchange resin-containing material comprising an ion-exchange resin alone or a mixture of an ion-exchange resin and a metal. Wherein the ion-exchange resin-containing material is continuously distributed in the continuous pores from one surface of the sheet-shaped substrate to the entire thickness direction, and decreases from one surface to the other surface. An ion exchange resin-containing sheet electrode material having a concentration gradient. 2. The sheet 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. Electrode material. 3. An ion-exchange resin-containing sheet electrode material according to claim 1 or 2, and a perfluorohydrocarbon-containing ion-exchange resin membrane layer, wherein the membrane layer comprises an ion-exchanged ion-exchange resin film. A sheet-like electrode composite material containing an ion-exchange resin, which is bound on one surface on which the exchange resin-containing material is distributed. 4. A binder comprising a fluorine-containing polymer,
From the mixture containing the carbon powder, a sheet-like substrate having a large number of continuous pores is formed, and one surface of the sheet-like substrate is brought into contact with a solution containing an ion exchange resin, and the solution is discharged from the one surface to the sheet-like substrate. Infiltrate and impregnate into continuous pores,
The impregnated body is subjected to a drying treatment, whereby the ion-exchange resin is continuously distributed from one surface of the sheet-like substrate into the continuous pores, and has a concentration gradient that decreases from one surface to the other surface. A method for producing a sheet-like electrode material containing an ion-exchange resin, comprising: 5. A binder comprising a fluorine-containing polymer,
From a mixture containing carbon powder, a sheet-like substrate having a large number of continuous pores is formed, one surface of the sheet-like substrate is brought into contact with a solution containing an ion exchange resin and a metal compound, and the solution is removed from the one surface. The continuous pores of the sheet-like substrate are impregnated and impregnated, the impregnated body is subjected to a drying treatment, and further subjected to a reduction treatment for the metal compound, whereby the mixture of the ion-exchange resin and the metal is mixed with the sheet-like material. A method for producing a sheet-like electrode material containing an ion-exchange resin, comprising: distributing continuously from one surface of the substrate into the continuous pores; and having a concentration gradient decreasing from one surface to the other surface.