JP2009059604A - HYBRID MEMBRANE FOR SOLID POLYMER FUEL CELL, PROCESS FOR PRODUCING THE SAME, MEMBRANE-ELECTRODE ASSEMBLE, PROCESS FOR PRODUCING THE SAME, AND SOLID POLYMER TYPE FUEL CELL - Google Patents

Abstract

The present invention provides a polymer electrolyte membrane that solves both the gas barrier property of the polymer electrolyte membrane and the chemical durability (radical resistance) of the polymer electrolyte membrane at the same time.
A hybrid membrane for a polymer electrolyte fuel cell in which a fluorine polymer electrolyte membrane and a hydrocarbon polymer electrolyte membrane are integrated by fusion bonding. In particular, a hybrid membrane for a solid polymer fuel cell, in which the fluorine polymer electrolyte membrane comprises a polymer electrolyte precursor (F type polymer electrolyte) that exhibits proton conductivity by hydrolysis.
[Selection] Figure 1

Description

  The present invention relates to a hybrid membrane for a polymer electrolyte fuel cell, a method for producing the same, a membrane-electrode assembly in which a catalyst-carrying gas diffusion electrode is bonded to both surfaces of an ion exchange membrane that can be used in a polymer electrolyte fuel cell, The present invention relates to a manufacturing method and a polymer electrolyte fuel cell having the same.

  Solid polymer fuel cells are expected as one of the pillars of future new energy technologies. A polymer electrolyte fuel cell (PEFC or PEMFC) using an ion exchange membrane made of a polymer as an electrolyte can be operated at a low temperature and can be reduced in size and weight. The application of is being considered. In particular, fuel cell vehicles equipped with polymer electrolyte fuel cells are gaining social interest as the ultimate ecological car.

  A solid polymer electrolyte is a solid polymer material having an electrolyte group such as a sulfonic acid group in a polymer chain, and has a property of binding firmly to a specific ion or selectively transmitting a cation or an anion. Have. In particular, a fluorine-based electrolyte membrane typified by a perfluorosulfonic acid membrane is awarded as an ion exchange membrane for fuel cells used under severe conditions because of its very high chemical stability.

  For example, a reformed gas fuel cell is provided with a pair of electrodes on both sides of a proton-conductive ion exchange membrane and hydrogen gas obtained by reforming low-molecular hydrocarbons such as methane and methanol as fuel gas. Is supplied to the other electrode (fuel electrode), and oxygen gas or air is supplied as an oxidizing agent to a different electrode (air electrode) to obtain an electromotive force.

  In the case of a fuel cell, peroxide is generated in the catalyst layer formed at the interface between the ion exchange membrane and the electrode, and the generated peroxide diffuses into a peroxide radical to cause a degradation reaction. It is impossible to use a hydrocarbon-based electrolyte membrane having poor properties. Therefore, perfluorosulfonic acid membranes having high proton conductivity are generally used in fuel cells and water electrolysis.

Currently, as ion exchange membranes used in polymer electrolyte fuel cells, Nafion (registered trademark) from DuPont, Flemion (registered trademark) from Asahi Glass, and Aciplex (registered trademark) from Asahi Kasei. A fluorocarbon sulfonic acid membrane is used.
In order to apply these ion exchange membranes to a polymer electrolyte fuel cell, a catalyst having a fuel oxidizing ability and an oxidizing agent reducing ability is disposed on both sides of the ion exchange membrane, and a gas diffusion electrode is provided outside thereof. Is used.

  That is, the structure forms a catalytic reaction layer mainly composed of carbon powder carrying a platinum-based metal catalyst on both surfaces of an ion exchange membrane made of a polymer electrolyte membrane that selectively transports hydrogen ions. Next, a gas diffusion layer having both fuel gas permeability and electronic conductivity is formed on the outer surface of the catalytic reaction layer. Generally, carbon paper or carbon cloth is used for the gas diffusion layer. The catalyst reaction layer and the gas diffusion layer described above are collectively referred to as an electrode.

  Next, in order to prevent leakage of the fuel gas to be supplied and to prevent mixing of the two types of fuel gas, a gas seal material and a gasket are arranged around the electrode with an ion exchange membrane interposed therebetween. This gas seal material or gasket is integrated with an electrode and an ion exchange membrane and assembled in advance, and is called a membrane-electrode assembly (MEA).

  On the outside of the MEA, a separator having electrical conductivity and airtightness for mechanically fixing the MEA and electrically connecting adjacent MEAs to each other in series is disposed. In the portion of the separator that contacts the MEA, a reaction gas is supplied to the electrode surface to form a gas flow path for carrying away the generated gas and surplus gas. Although the gas channel can be provided separately from the separator, a method of providing a gas channel by providing a groove on the surface of the separator is generally used. A structure in which the MEA is fixed by the pair of separators is referred to as a unit cell as a basic unit.

  A plurality of the unit cells are connected in series, and a manifold which is a piping jig for supplying fuel gas is arranged to constitute a fuel cell.

By the way, in the polymer electrolyte fuel cell (PEFC), during power generation, (1) the H ₂ gas on the anode side permeates through the membrane and directly reacts with the O ₂ gas on the cathode catalyst, resulting in a decrease in cell performance. (2) There was a problem that the electrolyte membrane was chemically deteriorated by H ₂ O ₂ generated by the side reaction on the cathode side, and the cell durability was lowered.

  The reason why the above problem occurs is that (1) is a problem of gas barrier property of the film, and (2) is a problem of chemical durability (radical resistance) of the film.

  The two mainstream electrolyte membranes for PEFC are hydrocarbon electrolyte membranes and fluorine electrolyte membranes. Hydrocarbon electrolyte membranes have excellent gas barrier properties but poor radical resistance. On the other hand, fluorine electrolyte membranes have excellent radical resistance but poor gas barrier properties. That is, there is no convenient film that can solve the above two problems at the same time.

  The characteristics of these hydrocarbon electrolyte membrane and fluorine electrolyte membrane are shown in Table 1 below.

  At present, there is no film excellent in both chemical durability and gas barrier properties.

  A fluorine-based electrolyte membrane typified by a perfluorosulfonic acid membrane has a very high chemical stability because it has a C—F bond. In addition to the fuel cell described above, an ion exchange membrane for salt electrolysis, It is also used as a solid polymer electrolyte membrane for hydrohalic acid electrolysis, and further applied to humidity sensors, gas sensors, oxygen concentrators, etc. by utilizing proton conductivity.

  However, the fluorine-based electrolyte is difficult to manufacture, has a drawback that it is very expensive and has low heat resistance. Therefore, the fluorine-based electrolyte membrane has been difficult to be applied to consumer use such as a polymer electrolyte fuel cell as a low-pollution power source for automobiles.

  On the other hand, the hydrocarbon-based electrolyte membrane has advantages in that it is easy to manufacture and low in cost as compared with a fluorine-based electrolyte membrane represented by Nafion. Therefore, various attempts have been made in the past to obtain a solid polymer electrolyte membrane that has oxidation resistance equivalent to or higher than that of a fluorine-based electrolyte membrane and can be produced at low cost.

  For example, the following Patent Document 1 discloses a sulfonic acid type polystyrene composed of a main chain made by copolymerization of a fluorocarbon vinyl monomer and a hydrocarbon vinyl monomer, and a hydrocarbon side chain having a sulfonic acid group. -Graft-ethylene-tetrafluoroethylene copolymer (ETFE) membranes have been proposed. In addition, by introducing a crosslink into a sulfonic acid type polystyrene graft resin membrane similar to the sulfonic acid type polystyrene-graft-ETFE membrane described above, desorption of low molecular weight components during oxidative degradation is suppressed, and an electrolyte for a fuel cell Attempts have been made to improve the durability of the membrane.

  Further, in Patent Documents 2 and 3 below, α, β, β-trifluorostyrene is graft-polymerized on a film made by copolymerization of a fluorocarbon vinyl monomer and a hydrocarbon vinyl monomer, and a sulfonic acid group is added thereto. A sulfonic acid type poly (trifluorostyrene) -graft-ETFE membrane has been proposed in which a solid polymer electrolyte membrane is introduced. This is based on the recognition that the chemical stability of the polystyrene side chain introduced with the sulfonic acid group is not sufficient, instead of styrene, α, β, β-trifluorostyrene obtained by fluorinating styrene. Is used.

  In addition, as the hydrocarbon-based ion exchange membrane, sulfonated polyether ether ketone (the following Patent Document 4 etc.), sulfonated polyethersulfone (the following Patent Document 5 etc.), sulfonated polysulfone (the following Patent Document 6 etc.), Sulfonated heat-resistant aromatic polymers such as sulfonated polyphenylene sulfide (such as Patent Document 7 below) and sulfonated polyimide (such as Patent Document 8 below), and SEBS (styrene- (ethylene-butylene) -styrene). Proton conductive membranes (such as Patent Document 10 below) composed of a sulfonated product (such as Patent Document 9 below) and a composite material of a proton conductivity-imparting agent and an organic polymer compound have also been proposed.

  However, these hydrocarbon ion exchange membranes are required to have high conductivity, contain many sulfonic acid groups, and need to be humidified in order to exhibit high conductivity. In addition, it has the property of being easily swelled with water. Therefore, when humidifying during power generation, the hydrocarbon-based ion exchange membrane swells, and there is a problem that the ion exchange membrane and the electrode catalyst layer are separated.

JP-A-9-102322 US Pat. No. 4,012,303 US Pat. No. 4,605,685 JP-A-6-93114 Japanese Patent Laid-Open No. 10-45913 JP-A-9-245818 Japanese National Patent Publication No. 11-510198 JP 2000-510511 A Japanese National Patent Publication No. 10-503788 JP 2000-90946 A

  An object of this invention is to provide the polymer electrolyte membrane which solves both the gas barrier property of a polymer electrolyte membrane, and the chemical durability (radical resistance) of a polymer electrolyte membrane simultaneously.

  The inventor has the advantages of both hydrocarbon polymer electrolyte membranes and fluorine polymer electrolyte membranes. Hydrocarbon polymer electrolyte membranes have excellent gas barrier properties, and fluorine polymer electrolyte membranes have radical resistance. The present inventors have found that an excellent electrolyte membrane that can solve the above-mentioned problems simultaneously can be obtained by combining the two.

  That is, first, the present invention is an invention of a hybrid membrane for a polymer electrolyte fuel cell, which is a hybrid membrane in which a fluorine-based polymer electrolyte membrane and a hydrocarbon-based polymer electrolyte membrane are integrated by fusion bonding. .

  As the fluorine-based polymer electrolyte membrane, a polymer electrolyte precursor (F-type polymer electrolyte) that exhibits proton conductivity by hydrolysis, or a polymer electrolyte that already has a proton-conducting group (H-type polymer electrolyte) However, as will be described later, from the viewpoints of melt-bonding property and melting temperature, a polymer electrolyte precursor (F-type polymer electrolyte) that exhibits proton conductivity by hydrolysis is preferred in the present invention.

  Second, the present invention is an invention of a method for producing a hybrid membrane for a solid polymer fuel cell as described above, wherein a fluorine-based polymer electrolyte membrane and a hydrocarbon-based polymer electrolyte membrane are melt-bonded (hot pressed). It is characterized by being integrated.

  As described above, as the fluorine-based polymer electrolyte membrane, a polymer electrolyte precursor (F-type polymer electrolyte) that exhibits proton conductivity by hydrolysis is preferable.

The fluorine-based polymer electrolyte membrane (H-type polymer electrolyte) having —SO ₃ H groups has a glass transition point of about 90 ° C. and a thermal decomposition point of about 150 ° C. On the other hand, the hydrocarbon polymer electrolyte membrane is hard with a glass transition of 200 ° C. or higher. In order to improve the adhesiveness between the two, it is desired to perform melt-compression bonding at 200 ° C. or higher. If a fluorine-based polymer electrolyte membrane (H-type polymer electrolyte) is melt-bonded at 200 ° C. or higher, thermal decomposition of the fluorine-based polymer electrolyte membrane partially occurs, and the interface resistance between the two increases. It may cause a decrease in power generation performance. Therefore, in the method for producing a hybrid film of the present invention, it is possible to perform melt compression bonding (hot pressing) at a temperature of 200 ° C. or higher, and to improve the adhesion between them.

  Third, the present invention is an invention of a membrane-electrode assembly (MEA) for a polymer electrolyte fuel cell comprising a pair of electrode catalyst layers and a polymer electrolyte membrane sandwiched between the electrode catalyst layers, The polymer electrolyte membrane has a fluorine polymer electrolyte membrane on the cathode side and a hydrocarbon polymer electrolyte membrane on the anode side. The fluorine polymer electrolyte membrane and the hydrocarbon polymer electrolyte membrane are It is a hybrid film integrated by melt-bonding.

  As described above, as the fluorine-based polymer electrolyte membrane, a polymer electrolyte precursor (F-type polymer electrolyte) that exhibits proton conductivity by hydrolysis is preferable.

  Fourth, the present invention is an invention of a method for producing a membrane-electrode assembly (MEA) for a polymer electrolyte fuel cell comprising a pair of electrode catalyst layers and a polymer electrolyte membrane sandwiched between the electrode catalyst layers. A fluorine-based polymer electrolyte membrane on the cathode side and a hydrocarbon-based polymer electrolyte membrane on the anode side, and these fluorine-based polymer electrolyte membrane and hydrocarbon-based polymer electrolyte membrane are melt-bonded (hot) It is characterized by being pressed and integrated.

  Fifth, the present invention is an invention of a method for producing a membrane-electrode assembly (MEA) for a polymer electrolyte fuel cell comprising a pair of electrode catalyst layers and a polymer electrolyte membrane sandwiched between the electrode catalyst layers. A polymer electrolyte membrane comprising a fluorine polymer electrolyte membrane on the cathode side and a hydrocarbon polymer electrolyte membrane on the anode side, and comprising the fluorine polymer electrolyte membrane and the hydrocarbon polymer electrolyte membrane. It is characterized in that both sides of the membrane are sandwiched between a pair of electrode catalyst layers, and are integrated by fusion bonding (hot pressing). In this invention, in the production of a membrane-electrode assembly for a solid polymer fuel cell, not only a fluorine-based polymer electrolyte membrane and a hydrocarbon-based polymer electrolyte membrane, but also a pair of electrode catalyst layers are melt-bonded (hot-pressed) simultaneously. Press).

  As described above, the fluorine-based polymer electrolyte membrane is preferably a polymer electrolyte precursor (F-type polymer electrolyte) that exhibits proton conductivity by hydrolysis.

  Sixth, the present invention is a polymer electrolyte fuel cell having the membrane-electrode assembly described above.

  The polymer electrolyte membrane of the present invention has a fluorine polymer electrolyte membrane on the cathode side and a hydrocarbon polymer electrolyte membrane on the anode side. These fluorine polymer electrolyte membrane and hydrocarbon polymer By using a hybrid membrane in which the electrolyte membrane is integrated by melt compression, voltage drop due to direct reaction between permeated hydrogen and oxygen on the cathode side during fuel cell operation is suppressed, and electrolyte chemical degradation near the cathode is suppressed. . Thereby, the output performance and durability performance of the fuel cell are improved. In particular, the output voltage after durability is improved while maintaining the current density and ionic conductivity.

  In addition, when the fluoropolymer electrolyte membrane and the hydrocarbon polymer electrolyte membrane are integrated by melt-bonding, the interfacial resistance between the two decreases by high-temperature melt-bonding of the fluoropolymer electrolyte precursor. improves.

In FIG. 1, the schematic diagram of the membrane-electrode assembly (MEA) of this invention is shown. As shown in FIG. 1, a hydrocarbon-based polymer electrolyte membrane and a fluorine-based polymer electrolyte membrane are bonded together to produce a hybrid electrolyte membrane. Utilizing the advantages of both polymer electrolytes to improve battery performance. That is, a hydrocarbon-based film is disposed on the anode side to suppress H ₂ permeation, and a fluorine-based film is disposed on the cathode side to suppress chemical deterioration.

FIG. 2 shows an example of the production of the hybrid electrolyte membrane of the present invention. In FIG. 2, a fluorine-based electrolyte membrane (H-type polymer electrolyte) having a proton exchange group-SO ₃ H group is already used as the fluorine-based polymer electrolyte membrane, and the H-type polymer electrolyte membrane and the hydrocarbon-based polymer electrolyte are used. The film is melt bonded by hot pressing. In this case, the H-type polymer electrolyte has a glass transition point of about 90 ° C. and a thermal decomposition point of about 150 ° C. On the other hand, the hydrocarbon electrolyte membrane is hard with a glass transition of 200 ° C. or higher. In order to improve the adhesiveness between the two, it is desired to perform melt-compression bonding at 200 ° C. or higher. However, since the thermal decomposition point of the fluorine electrolyte membrane is 150 ° C., the problem remains that it cannot be achieved.

FIG. 3 shows another example of the production of the hybrid electrolyte membrane of the present invention. In FIG. 3, a fluorine-based electrolyte membrane (F-type polymer electrolyte) having —SO ₂ F type before protonation is used, and the F-type polymer electrolyte membrane and the hydrocarbon-based polymer electrolyte membrane are melt-bonded by hot pressing. To do. In this case, since the F-type polymer electrolyte has a glass transition point of room temperature or lower, a thermal decomposition point of about 300 ° C., and a softening point of about 200 ° C., the glass transition of the hydrocarbon electrolyte membrane is 200 ° C. or higher. Can be melt-bonded. For this reason, both adhesiveness improves.

Among the fluorine-based polymer electrolytes used in the present invention, a proton-conducting polymer electrolyte (referred to as an H-type polymer electrolyte) has a sulfonic acid group and the like, and is itself not particularly modified in a later step. It has proton conductivity. The polymer electrolyte precursor that exhibits proton conductivity by hydrolysis used in the present invention (simply referred to as polymer electrolyte precursor or F-type polymer electrolyte) is a hydrolysis treatment or acidification treatment in a later step. And a precursor group that is modified to a proton conductive group such as a sulfonic acid group, for example, a —SO ₂ F group, a —SO ₂ Cl group, and the like.

  In the present invention, the hydrocarbon-based polymer electrolyte means one having a C—H bond in any of the molecular chains and capable of introducing an electrolyte group. The electrolyte group means a functional group having an electrolyte ion such as a sulfonic acid group or a carboxylic acid group.

  Specific examples of the hydrocarbon polymer electrolyte include polyethersulfone resin, polyetheretherketone resin, linear phenol-formaldehyde resin, cross-linked phenol-formaldehyde resin, linear polystyrene resin, cross-linked polystyrene resin, Chain-type poly (trifluorostyrene) resin, cross-linked (trifluorostyrene) resin, poly (2,3-diphenyl-1,4-phenylene oxide) resin, poly (allyl ether ketone) resin, poly (arylene ether sulfone) ) Resin, poly (phenylquinosanline) resin, poly (benzylsilane) resin, polystyrene-graft-ethylenetetrafluoroethylene resin, polystyrene-graft-polyvinylidene fluoride resin, polystyrene-graft-tetrafluoroethylene resin, etc. And the like to.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited by these Examples.

  About the polymer electrolyte membrane of the following specification, after transferring the electrode catalyst by a predetermined method, the paper diffusion layer was bonded, and the output performance and durability performance were compared and evaluated.

[Comparative Example 1]
The anode / cathode electrode layer was bonded to Nafion 1000 (trade name) 20 μm.

[Comparative Example 2]
A sulfonated polyetherketone membrane, which is a hydrocarbon polymer electrolyte membrane, was used, and an anode / cathode electrode layer was bonded thereto.

[Example 1]
A hybrid membrane was prepared by hot-pressing a fluorinated polymer electrolyte membrane, Nafion 1000 (trade name), and a sulfonated polyetherketone membrane, a hydrocarbon polymer electrolyte membrane, at 130 ° C. The anode / cathode electrode layer was joined to this.

[Example 2]
After hot-pressing a Nafion 1000 (trade name) precursor (side chain end-SO ₂ F type) and a sulfonated polyetherketone membrane at 230 ° C., a hybrid membrane obtained by protonating —SO ₂ F by alkali / acid treatment Produced. The anode / cathode electrode layer was joined to this.

Here, in each comparative example and example, the film thickness and the catalyst area were all adjusted to the same level.
Table 2 below shows the initial output voltage at each current density. Table 3 below shows the output voltage @ 0.1 A / cm ² with respect to the durability time.

  FIG. 4 compares the ionic conductivity of each electrolyte membrane when saturated with water.

  From the results of Tables 2, 3 and 4, the fuel cell using the hybrid membrane of the present invention is a conventional fuel that uses only a fluorine-based polymer electrolyte or only a hydrocarbon-based polymer electrolyte as a polymer electrolyte exchange membrane. It can be seen that the power generation performance is improved compared to the battery. In particular, the fuel cell using the hybrid membrane of Example 2 using a polymer electrolyte precursor (F-type polymer electrolyte) that exhibits proton conductivity by hydrolysis and melt-bonded at a high temperature has a current density and ionic conductivity. It can be seen that the output voltage after durability is improved while maintaining the above.

A hybrid membrane in which a hydrocarbon polymer electrolyte membrane and a fluorine polymer electrolyte membrane are fused and bonded together is used, a fluorine polymer electrolyte membrane having high chemical durability is disposed on the cathode side, and H ₂ is disposed on the anode side. By arranging the low-permeability hydrocarbon-based polymer electrolyte membrane, the output performance and durability performance of the fuel cell are improved. In particular, the output voltage after durability can be improved while maintaining the current density and ionic conductivity. This contributes to the practical application and spread of fuel cells.

The schematic diagram of the membrane-electrode assembly (MEA) of this invention is shown. An example of a fabrication of a hybrid electrolyte film using a fluorine-based polymer electrolyte membrane having a proton exchange group -SO 3 _H type (H-type polymer electrolyte). An example of producing a hybrid electrolyte membrane using a fluorine-based polymer electrolyte membrane (F-type polymer electrolyte) having —SO ₂ F type before protonation is shown. The graph which compared the ionic conductivity of each polymer electrolyte membrane at the time of saturated water content is shown.

Claims (11)

  A hybrid membrane for a polymer electrolyte fuel cell in which a fluorine polymer electrolyte membrane and a hydrocarbon polymer electrolyte membrane are integrated by fusion bonding.   2. The polymer electrolyte fuel cell according to claim 1, wherein the fluorine-based polymer electrolyte membrane is made of a polymer electrolyte precursor (F-type polymer electrolyte) that exhibits proton conductivity by hydrolysis. Hybrid membrane.   A method for producing a hybrid membrane for a polymer electrolyte fuel cell, characterized in that a fluorine-based polymer electrolyte membrane and a hydrocarbon-based polymer electrolyte membrane are integrated by fusion-compression (hot pressing).   4. The polymer electrolyte fuel cell according to claim 3, wherein the fluorine-based polymer electrolyte membrane is made of a polymer electrolyte precursor (F-type polymer electrolyte) that exhibits proton conductivity by hydrolysis. A method for producing a hybrid membrane.   The method for producing a hybrid membrane for a polymer electrolyte fuel cell according to claim 3 or 4, wherein the melt-bonding (hot pressing) is performed at a temperature of 200 ° C or higher.   A membrane-electrode assembly (MEA) for a polymer electrolyte fuel cell comprising a pair of electrode catalyst layers and a polymer electrolyte membrane sandwiched between the electrode catalyst layers, the polymer electrolyte membrane on the cathode side A hybrid membrane in which a fluorine-based polymer electrolyte membrane is disposed, a hydrocarbon-based polymer electrolyte membrane is disposed on the anode side, and these fluorine-based polymer electrolyte membrane and hydrocarbon-based polymer electrolyte membrane are integrated by fusion bonding. A membrane-electrode assembly for a polymer electrolyte fuel cell, characterized in that it exists.   7. The polymer electrolyte fuel cell according to claim 6, wherein the fluorine-based polymer electrolyte membrane is made of a polymer electrolyte precursor (F-type polymer electrolyte) that exhibits proton conductivity by hydrolysis. Membrane-electrode assembly.   A method for producing a membrane-electrode assembly (MEA) for a polymer electrolyte fuel cell comprising a pair of electrode catalyst layers and a polymer electrolyte membrane sandwiched between the electrode catalyst layers, the fluorine-based polymer on the cathode side An electrolyte membrane is arranged, a hydrocarbon polymer electrolyte membrane is arranged on the anode side, and the fluorine polymer electrolyte membrane and the hydrocarbon polymer electrolyte membrane are integrated by fusion bonding (hot pressing). A method for producing a membrane-electrode assembly for a polymer electrolyte fuel cell.   A method for producing a membrane-electrode assembly (MEA) for a polymer electrolyte fuel cell comprising a pair of electrode catalyst layers and a polymer electrolyte membrane sandwiched between the electrode catalyst layers, the fluorine-based polymer on the cathode side An electrolyte membrane is disposed, a hydrocarbon polymer electrolyte membrane is disposed on the anode side, and a pair of electrode catalyst layers are disposed on both sides of the polymer electrolyte membrane composed of the fluorine polymer electrolyte membrane and the hydrocarbon polymer electrolyte membrane. A method for producing a membrane-electrode assembly for a polymer electrolyte fuel cell, wherein the membrane-electrode assembly is sandwiched between and integrated by melt-compression (hot pressing).   The solid polymer fuel according to claim 8 or 9, wherein the fluorine-based polymer electrolyte membrane comprises a polymer electrolyte precursor (F-type polymer electrolyte) that exhibits proton conductivity by hydrolysis. A method for producing a membrane-electrode assembly for a battery.   A polymer electrolyte fuel cell comprising the membrane-electrode assembly according to claim 6 or 7.

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