WO2003088396A1 - Solid polymer electrolyte fuel battery having improved performance and reliability and manufacturing method thereof - Google Patents

Abstract

A fuel battery includes a solid polymer electrolyte film (114) formed by a first solid polymer electrolyte and catalyst electrodes (102, 108) attached to a rough surface. Here, the solid polymer electrolyte film (114) has a rough surface. The catalyst electrodes (102, 108) have catalyst layers (106, 112) and substrate layers (104, 110) holding the catalyst layers (106, 112). The catalyst layers (106, 112) contain a catalyst and a second solid polymer electrolyte. The catalyst layers (106, 112) are attached to the rough surface. The rough surface has a contour curve having an arithmetic average height (Ra) as follows: 0.5 ≤ nm Ra ≤ 100 nm. The contour curve elements of the rough surface have an average length (RSm) as follows: 0.5 ≤ nm RSm ≤ 1000 nm. However, the Ra and the RSm are defined by the JIS-B0601-2001 (ISO4287-1997).

Description

 TECHNICAL FIELD The present invention relates to a solid polymer electrolyte fuel cell having improved performance and reliability, and a method for producing the same.

 The present invention relates to a solid polymer electrolyte fuel cell, a solid polymer electrolyte membrane for a fuel cell, and a method for producing the same, and particularly to a solid polymer electrolyte fuel cell and a fuel cell with improved performance and reliability. The present invention relates to solid polymer electrolyte membranes and methods for producing them. Background art

 The polymer electrolyte fuel cell is composed of a solid polymer electrolyte membrane such as a perfluorosulfonate membrane as an electrolyte, and a fuel electrode and an oxidizer electrode joined to both sides of this membrane. This is a device that supplies oxygen to the poles and generates power by an electrochemical reaction.

 The following electrochemical reaction occurs in each electrode.

Fuel electrode: H 2 → 2 H ++ 2 e

Oxidant electrode: l Z 2〇2 + 2 H ++ 2 e-"20

 By this reaction, the polymer electrolyte fuel cell can obtain a high output of 1 A / cm 2 or more at normal temperature and normal pressure.

 The fuel electrode and the oxidizer electrode are provided with a mixture of carbon particles carrying a catalytic substance and a solid polymer electrolyte. In general, the mixture is applied to an electrode substrate such as a pressure-sensitive paper, which serves as a fuel gas diffusion layer. A fuel cell is constructed by sandwiching the polymer electrolyte membrane between these two electrodes and thermocompression bonding.

 In the fuel cell having this configuration, the hydrogen gas supplied to the fuel electrode passes through the pores in the electrode, reaches the catalyst, and emits electrons to become hydrogen ions. The emitted electrons are led to the external circuit through the carbon particles in the fuel electrode and the electrode substrate, and flow into the oxidizer electrode from the external circuit.

 On the other hand, hydrogen ions generated at the fuel electrode reach the oxidizer electrode through the solid polymer electrolyte in the fuel electrode and the solid polymer electrolyte membrane disposed between both electrodes, and are supplied to the oxidizer electrode. Reacts with the electrons flowing from the external circuit to produce water as shown in the above reaction formula. As a result, in the external circuit, electrons flow from the fuel electrode to the oxidizer electrode, and power is extracted.

In order to improve the characteristics of the fuel cell having the above configuration, it is important that the adhesion between the electrode and the solid polymer electrolyte membrane be good. In other words, it is necessary that the conductivity of hydrogen generated by the electrode reaction be high at the interface between the two. Required. Poor interfacial adhesion reduces the conductivity of hydrogen ions and increases electrical resistance, causing a reduction in battery efficiency.

 The fuel cell using hydrogen as a fuel has been described above. In recent years, research and development of fuel cells using an organic liquid fuel such as methanol have been actively conducted.

 Fuel cells that use organic liquid fuel include those that reform organic liquid fuel into hydrogen gas and use it as fuel, and those that reform organic liquid fuel, such as direct methanol fuel cells. It is known to supply the fuel directly to the fuel electrode without using it.

 Above all, a fuel cell that supplies organic liquid fuel directly to the anode without reforming it does not require a device such as a reformer because it has a structure that supplies organic liquid fuel directly to the anode. Therefore, there is an advantage that the configuration of the battery can be simplified and the entire device can be reduced in size. In addition, organic liquid fuels can be easily and safely transported compared to gaseous fuels such as hydrogen gas and hydrocarbon gas.

 Generally, in a fuel cell using an organic liquid fuel, a solid polymer electrolyte membrane made of a solid polymer ion exchange resin is used as an electrolyte. Here, in order for the fuel cell to function, it is necessary for hydrogen ions to move through the membrane from the fuel electrode to the oxidizer electrode, but the movement of hydrogen ions involves the movement of water. It is necessary that the film contains a certain amount of moisture.

 However, when an organic liquid fuel such as methanol having a high affinity for water is used, the organic liquid fuel diffuses into the solid polymer electrolyte membrane containing water and further reaches the oxidant electrode (crossing). Over). This crossover causes a reduction in voltage, output, and fuel efficiency because organic liquid fuel, which should originally provide electrons at the fuel electrode, is oxidized on the oxidant electrode side and is not used effectively as fuel. .

From the viewpoint of solving such a crossover problem, it is desirable to select a polymer having a low water content as the material of the solid polymer electrolyte membrane and to suppress the diffusion of an organic liquid fuel such as methanol with water. . However, for the catalyst layer on the electrode surface in contact with the solid polymer electrolyte membrane, it is important to efficiently move the organic liquid fuel as the fuel from the electrode layer and supply a large amount of hydrogen ions. That is, it is desirable that the catalyst layer on the electrode surface is permeable to the organic liquid fuel and that the electrolyte membrane is permeable to the organic liquid fuel. In order to achieve this, the polymer constituting the catalyst layer on the electrode surface must be a polymer having a high water content and high permeability to organic liquid fuel, and the polymer constituting the solid polymer electrolyte membrane must be used. It is considered preferable to use a material having a low water content and a property of low permeability of organic liquid fuel. However, when the material of the electrode surface catalyst layer and the material of the solid polymer electrolyte membrane are different from each other as described above, generally, sufficient adhesion cannot be obtained, and the interface between the electrode surface and the solid polymer electrolyte membrane is generally not obtained. May cause peeling. When such peeling occurs, the electrical resistance at the interface increases, causing a decrease in the reliability of the battery performance.

 As a related technique, Japanese Patent Application Laid-Open No. H11-222422 discloses a technique of a polymer electrolyte fuel cell.

 The polymer electrolyte fuel cell according to this technique includes a polymer electrolyte layer, an electrode layer, and a partition member. The solid polymer electrolyte layer transmits predetermined ions and has a film shape. The electrode layers are provided on both sides of the solid polymer electrolyte layer, respectively, and are conductive. The partition member faces the respective electrode layers and forms a fuel gas chamber and an oxidizing gas chamber between the respective electrode layers. The solid polymer electrolyte layer and the electrode layer are formed into an uneven shape, and have a rigid shape holder that holds the uneven shape.

 This technology is to provide a polymer electrolyte fuel cell with higher power generation capacity per unit volume and lower manufacturing cost.

 Japanese Patent Application Laid-Open No. Hei 9-63632 discloses a technique of a method for manufacturing a polymer electrolyte fuel cell.

 The method for manufacturing a polymer electrolyte fuel cell according to this technique includes providing a first catalyst layer on one surface of a solid polymer electrolyte membrane, and forming an electrode base on one of an anode electrode and a force source electrode. Providing a second catalyst layer on the surface of the material; and superposing one of the anode electrode and the cathode electrode on the first catalyst layer, and forming the other on the other surface of the solid polymer electrolyte membrane. The method includes a step of laminating the second catalyst layer of the one electrode and pressing and integrating the electrodes with the solid polymer electrolyte membrane.

 At that time, a mixture obtained by kneading either one of the fluoropolymer or its suspension and the catalyst particles is applied to the surface of the electrode substrate, and heat-treated at a temperature equal to or higher than the melting point of the fluoropolymer, Further, the second catalyst layer may be provided by applying a dispersion of a solid polymer electrolyte membrane to the surface of the electrode substrate.

 The purpose of this technique is to provide a method for manufacturing a polymer electrolyte fuel cell that avoids loss due to short circuit while maintaining cell performance.

 Japanese Patent Application Laid-Open No. 2000-2006 discloses a technique of a gas diffusion electrode-electrolyte membrane assembly.

In the gas diffusion electrode-electrolyte membrane assembly according to this technique, a porous electrolyte layer having three-dimensionally communicating pores is formed on at least one surface of the electrolyte membrane. Then, a gas diffusion electrode is joined on the porous electrolyte layer. Platinum for porous electrolyte layer T JP03 / 04815

Group metal is supported.

 The platinum group metal supported on the porous electrolyte layer may be mainly distributed near the surface of the porous electrolyte layer.

 The purpose of this technology is to increase the contact area of the interface between the electrolyte membrane of the gas diffusion electrode-electrolyte membrane assembly and the catalyst, and to mix impurities and reduce degradation of the electrolyte in order to increase the output of the fuel cell. An object of the present invention is to provide a gas diffusion electrode-electrolyte membrane assembly which does not cause a decrease in ionic conductivity.

 Japanese Unexamined Patent Publication No. 2000-285932 discloses a technique of a method for producing an electrode-membrane assembly for a polymer electrolyte fuel cell.

 The method for producing an electrode and a membrane assembly for a polymer electrolyte fuel cell according to this technique is based on a method of applying an ion-exchange membrane by applying a coating solution containing an ion-exchange resin onto an electrode layer formed on a support. After forming two films on which the ion exchange membranes are bonded inward, the two support members are separated from the electrode layer.

 The electrode layer may be formed by applying a coating solution containing a catalyst and an ion exchange resin on the support and drying the coating.

 An object of this technology is to provide a method for efficiently producing an electrode / membrane assembly having high bonding strength in a polymer electrolyte fuel cell. '

 Japanese Patent Application Laid-Open No. Hei 9-171889 discloses a technology of an electrolytic functional element.

 The electrolytic function device of this technology includes a solid polymer electrolyte membrane, a pair of base materials, and a catalyst layer. The pair of substrates have a plurality of through-holes formed therein, and are formed of metal plates embedded on the front and back sides of the solid polymer electrolyte membrane so as to sandwich the solid polymer electrolyte membrane, and a DC power supply voltage is supplied from outside. Make electrodes. The catalyst layer is formed so as to cover the outer surfaces of the pair of base materials and the surface of the solid polymer electrolyte membrane present in each through hole of the base materials. Promote the reaction.

 It is an object of the present invention to provide an electrolytic functional element having a structure in which the anode, the cathode, the catalyst layer, and the solid polymer electrolyte membrane are not easily peeled off without using a holding jig, and a method for manufacturing the same. Disclosure of the invention

 In view of the above circumstances, an object of the present invention is to increase the adhesion at the interface between the surface of a catalyst electrode and a solid polymer electrolyte membrane, to improve battery characteristics and battery reliability.

Another object of the present invention is to suppress the crossover of the organic liquid fuel while maintaining the hydrogen ion conductivity and the transparency of the organic liquid fuel on the surface of the catalyst electrode in a good condition. Hereinafter, the means for solving the problem will be described using the numbers and symbols used in [Best Mode for Carrying Out the Invention]. These numbers and symbols are added in parentheses to clarify the correspondence between the description in the claims and the best mode for carrying out the invention. However, those numbers and signs should not be used for interpreting the technical scope of the invention described in [Claims]. In order to solve the above-mentioned problems, a fuel cell of the present invention comprises a solid polymer electrolyte membrane (114) formed of a first solid polymer electrolyte, and a catalyst electrode (102, 108) joined to an uneven surface thereof. And

 Here, the solid polymer electrolyte membrane (114) has an uneven surface.

 In the above fuel cell, the catalyst electrode (102, 108) includes a catalyst layer (106, 112) and a base layer (104, 110) holding the catalyst layer (106, 112). The catalyst layer (106, 112) includes a catalyst substance and a second solid polymer electrolyte.

 Then, the catalyst layer (106, 112) and its uneven surface are joined.

 In the above fuel cell, the arithmetic mean height (Ra) of the contour curve on the uneven surface has a value of 0.5 nm≤Ra≤100 nm. Ra is J I S—B 0

601-2001 (IS04287-1997).

 In the above fuel cell, the average length (R

Sm) has a value of 0.5 nm≤RSm≤1000 nm. RSm is specified in JIS-B0601-2001 (IS04287-1997).

 In the above fuel cell, the second solid polymer electrolyte is made of a polymer compound or a derivative thereof constituting the first solid polymer electrolyte. The polymer compound and its derivative have a water content lower than a reference water content set in advance so as to suppress crossover.

 In the above fuel cell, the polymer compound contains at least one of sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) and alkylsulfonated polybenzimidazole.

 In the above fuel cell, the water content of the second solid polymer electrolyte is higher than the water content of the first solid polymer electrolyte.

 In the above fuel cell, the first solid polymer electrolyte contains at least one of sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) and alkylsulfonated polybenzimidazole. . The second solid polymer electrolyte contains at least one of a sulfone group-containing perfluorocarbon and a sulfonic acid group-containing perfluorocarbon.

In order to solve the above problems, a method for producing a solid polymer electrolyte membrane for a fuel cell according to the present invention comprises steps (a) to (b). (A) The step is PC leakage 815

Provide a disintegrating membrane (114). (B) roughening at least one surface of the solid polymer electrolyte membrane (114);

 In the method for producing a solid polymer electrolyte membrane for a fuel cell described above, the step (b) includes the step of rubbing a fiber on at least one surface of the solid polymer electrolyte membrane (114).

 In the above-described method for producing a solid polymer electrolyte membrane for a fuel cell, the step (b) includes the step of: (b 2) performing ion irradiation on at least one surface of the solid polymer electrolyte membrane (114). .

 In the above method for producing a solid polymer electrolyte membrane for a fuel cell, the step (b) comprises (b3) performing a plasma treatment step on at least one surface of the solid polymer electrolyte membrane (114). .

 In the above method for producing a solid polymer electrolyte membrane for a fuel cell, the arithmetic average height (Ra) of the contour curve of the uneven surface on the surface of the solid polymer electrolyte membrane (114) is 0.5 nm≤Ra≤ It has a value of 100 nm. Ra is specified in JIS—B0601-2001 (IS04287—1997).

 In the method for producing a solid polymer electrolyte membrane for a fuel cell described above, the average length (RSm) of the contour curve element of the uneven surface on the surface of the solid polymer electrolyte membrane (114) is 0.5 nm≤RSm≤1000 It has a value of nm. RSm is specified in JIS-B0601-2001 (ISO4287-1997).

 In order to solve the above problems, a method for manufacturing a fuel cell according to the present invention includes steps (c) to (e). The step (c) roughens the surface of the solid polymer electrolyte membrane (114) formed of the first solid polymer electrolyte. In the step (d), a catalyst electrode (102, 108) including a catalyst substance and a second solid polymer electrolyte is produced. (E) In the step, the catalyst electrodes (102, 108) are bonded to the surface of the solid polymer electrolyte membrane (114).

 In the above-described method for producing a fuel cell, the step (d) includes a step (d1) of applying a coating solution onto the base (104, 110) to form a catalyst layer (106, 112). Here, the coating liquid contains conductive particles carrying the catalyst substance and particles containing the second solid polymer electrolyte.

 The (e) step includes: (e 1) bringing the surface of the solid polymer electrolyte membrane (114) into contact with the surface of the catalyst electrode (102, 108); and (e2) the solid polymer electrolyte membrane ( 11) and the step of crimping the catalyst electrode (102, 108).

In the above-described method for producing a fuel cell, the second solid polymer electrolyte comprises a polymer conjugate or a derivative thereof constituting the first solid polymer electrolyte. The polymer conjugate and the derivative have a water content that suppresses crossover. Is lower than the reference moisture content set in advance.

 In the above method for producing a fuel cell, the polymer compound is at least one of sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) and alkylsulfonated polybenzimidazole. including.

 In the above fuel cell, the second water content of the second solid polymer electrolyte is higher than the first water content of the first solid polymer electrolyte.

 In the above method for producing a fuel cell, the first solid polymer electrolyte comprises at least one of sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) and alkyl sulfonated polybenzoimidazole. Including one. The second solid polymer electrolyte contains at least one of perfluorocarbon containing a sulfone group and perfluorocarbon containing a lipoxyl group. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a sectional view schematically showing a single cell structure of a fuel cell according to an embodiment of the present invention.

 FIG. 2 is a cross-sectional view schematically showing a fuel electrode, an oxidizer electrode, and a solid polymer electrolyte membrane in an example of the fuel cell of the present invention.

 FIG. 3 is a flowchart showing a method of manufacturing a fuel cell according to the embodiment of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the solid polymer electrolyte fuel cell and the method for producing the same according to the present invention will be described in detail.

 A fuel cell according to the present invention includes a fuel electrode, an oxidizer electrode, and a solid polymer electrolyte membrane, and the solid polymer electrolyte membrane has an uneven surface on at least one surface. The fuel electrode and the oxidizer electrode are collectively called a catalyst electrode. The uneven surface may be formed on the entire surface of one surface of the solid polymer electrolyte membrane, or may be formed on a part thereof.

 FIG. 1 is a cross-sectional view schematically showing a single cell structure of a fuel cell according to an embodiment of the present invention. The fuel cell 100 has a plurality of single cell structures 101. Each unit cell structure 101 is composed of a fuel electrode 102, an oxidant electrode 108, and a solid polymer electrolyte membrane 114. Fuel 124 is supplied to the fuel electrode 102 of each single cell structure 101 via the fuel electrode side end plate 120. In addition, the oxidizing agent electrode 126 of each single cell structure 101 is supplied with the oxidizing agent 126 via the oxidizing agent electrode side end plate 122.

Figure 2 shows the fuel electrode 102, the oxidizer electrode 108, and the solid polymer electrolyte membrane 1 FIG. 14 is a cross-sectional view schematically showing the structure of FIG.

 The solid polymer electrolyte membrane 114 has a role of separating the fuel electrode 102 and the oxidant electrode 108 and of transferring hydrogen ions between the two. For this reason, the solid polymer electrolyte membrane 114 is preferably a membrane having high hydrogen ion conductivity and high water mobility. Further, it is preferable that it is chemically stable and has high mechanical strength. Examples of the material constituting the solid polymer electrolyte membrane 114 include an organic polymer having a polar group such as a strong acid group such as a sulfone group, a phosphate group, a phosphone group, or a phosphine group, or a weak acid group such as a lipoxyl group. It is preferably used. Examples of such organic polymers include aromatic-containing polymers such as sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) and alkylsulfonated polybenzoimidazole; polystyrenesulfonic acid copolymer. Copolymers such as copolymers, polyvinyl sulfonic acid copolymers, cross-linked alkyl sulfonic acid derivatives, fluororesin skeletons, and fluorine-containing polymers composed of sulfonic acids; acrylamides such as 2-methylpropanesulfonic acid and n- Copolymer obtained by copolymerizing acrylates such as butyl methacrylate; sulfone-containing perfluorocarbon (Nafion (DuPont: registered trademark), Aciplex (Asahi Kasei: registered trademark)); Group-containing perfluorocarbon (Flemion S membrane (made by Asahi Glass Co., Ltd.)); There are exemplified. Of these, when aromatic-containing polymers such as sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) and alkylsulfonated polybenzoimidazole are selected, organic liquid fuel Transmission can be suppressed, and a decrease in battery efficiency due to crossover can be suppressed.

 Further, the solid polymer electrolyte membrane 114 in the present invention has been subjected to a surface treatment (treatment for roughening the surface). Due to the surface treatment, the surface has an uneven structure. In addition, atoms bonded at or near the outermost surface of the solid polymer electrolyte membrane 114 are stripped off, and the surface activity is increased. Due to one or both of these effects, in the contact between the solid polymer electrolyte membrane 114 and the fuel electrode 102 or the oxidant electrode 108 (catalyst electrode), the adhesion at the interface is improved, and the battery characteristics are improved. And the reliability of the battery can be improved.

 The uneven surface of the solid polymer electrolyte membrane 114 may have, for example, an arithmetic mean height (R a) of a contour curve of preferably 0.5 nm or more, more preferably 1 nm or more. Further, Ra can be preferably 100 nm or less, more preferably 50 nm or less. Thereby, the adhesion to the catalyst electrode surface is remarkably improved.

The uneven surface of the solid polymer electrolyte membrane 114 may have, for example, an average length (RSm) of a contour curve element of the uneven surface of preferably 0.5 nm or more, more preferably 1 nm or more. RS m is preferably 100 nm or less, more preferably More preferably, it can be less than 10 Onm. This significantly improves the adhesion to the catalyst electrode surface.

 Here, the arithmetic average height (Ra) of the contour curve and the average length (R Sm) of the contour curve element are defined by JIS-B-0601-2001 (IS04287-1997). And it can be measured using, for example, an atomic force microscope (AFM).

 As shown in FIG. 2, the fuel electrode 102 and the oxidant electrode 108 in the present embodiment are formed of a catalyst layer 106 containing carbon particles carrying a catalyst and fine particles of a solid polymer electrolyte. The catalyst layer 112 is formed on the substrate 104 and the substrate 110. The substrate surface may be subjected to a water-repellent treatment.

 As the base 104 and the base 110, a porous base such as a carbon vapor, a carbon molded body, a carbon sintered body, a sintered metal, or a foamed metal can be used. Further, a water repellent such as polytetrafluoroethylene can be used for the water repellent treatment of the base 104 and the base 110.

 Examples of the catalyst for the anode 102 include platinum, alloys of platinum with ruthenium, gold, rhenium, and the like, rhodium, palladium, iridium, osmium, ruthenium, rhenium, gold, silver, nickel, cobalt, lithium, lanthanum, Examples include strontium and yttrium. On the other hand, as the catalyst for the oxidant electrode 108, the same catalyst as that for the fuel electrode 102 can be used, and the above-mentioned exemplified substances can be used. The catalysts for the fuel electrode 102 and the oxidant electrode 108 may be the same or different.

 Examples of carbon particles that carry the catalyst include acetylene black (Denka Black (registered trademark, manufactured by Denki Kagaku), XC72 (manufactured by Vulcan), etc.), ketchen black, carbon nanotubes, carbon nanohorn, Examples thereof include amorphous carbon. The particle diameters of carbon and particles are, for example, 0.01 to 0.1 m, preferably 0.02 to 0.06.

In the present invention, the solid polymer electrolyte constituting the fuel electrode 102 or the oxidizer electrode 108 electrically connects the catalyst-supporting carbon particles and the solid polymer electrolyte membrane 114 on the electrode surface and forms an organic polymer on the catalyst surface. It has the role of allowing liquid fuel to reach, and is required to have hydrogen ion conductivity and water mobility. In addition, the fuel electrode 102 requires organic liquid fuel permeability such as methanol, and the oxidizer electrode 1 08 requires oxygen permeability. The solid polymer electrolyte is intended to satisfy such requirements, and materials having excellent hydrogen ion conductivity and organic liquid fuel permeability such as methanol are preferably used. Specifically, an organic polymer having a polar group such as a strong acid group such as a sulfone group or a phosphate group or a weak acid group such as a carboxyl group is preferably used. Examples of such organic polymers include perfluorocarbons containing sulfone groups (Nafion (manufactured by DuPont) and Asiplex (manufactured by Asahi Kasei)); Copolymers such as lensulfonic acid copolymers, polyvinylsulfonic acid copolymers, cross-linked alkylsulfonic acid derivatives, fluorine-containing polymers composed of a fluororesin skeleton and sulfonic acid; acrylates such as acrylamide-2-methylpropanesulfonic acid And copolymers obtained by copolymerizing acrylamides and acrylates such as n-butyl methacrylate; and the like.

 Examples of the polymer to which the polar group is bonded include amine-substituted polystyrene such as polybenzimidazole derivative, polybenzoxazole derivative, polyethyleneimine cross-linked product, polysilamine derivative, polydimethylaminoethyl polystyrene, etc. Resins having nitrogen or hydroxyl groups such as nitrogen-substituted boria acrylates such as polystyrene and getyl aminoethyl polymethacrylate; hydroxyl-containing polyacrylic resins represented by silanol-containing polysiloxane and hydroxyethyl polymethyl acrylate; para-hydroxy polystyrene A representative hydroxyl group-containing polystyrene resin may be used.

 In addition, a crosslinkable substituent such as a vinyl group, an epoxy group, an acryl group, a methacryl group, a cinnamoyl group, a methylol group, an azide group, or a naphthoquinone diazide group may be appropriately introduced into the above-described polymer. Good.

 Here, from the viewpoint of suppressing the crossover, the solid polymer electrolyte membrane 114 and the solid polymer electrolyte in the fuel electrode 102 and the oxidizer electrode 108 are all composed of organic liquid fuel. It is preferable to use a material having low permeability (low moisture content). However, the water content shall be lower than the reference water content. For the reference moisture content, a value that can suppress crossover is determined experimentally based on the fuel cell design. These materials include, for example, aromatic condensed polymers such as sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) and alkylsulfonated polybenzoimidazole. preferable.

Furthermore, in order to achieve both the viewpoint of suppressing crossover (improving reliability) and the viewpoint of improving battery performance, it is preferable to set the characteristics of the solid polymer electrolyte as follows. That is, as the solid polymer electrolyte of the solid polymer electrolyte membrane 114, a material having low permeability (low water content) of the organic liquid fuel is used. Examples of such a material include aromatic condensed polymers such as sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) and alkylsulfonated polybenzimidazole. The catalyst layer on the surface of the electrode (the fuel electrode 102 or the oxidant electrode 108) in contact with the solid polymer electrolyte membrane 114 corresponding to the above-mentioned materials is prepared by changing the catalyst layer on the electrode surface. High permeability of organic liquid fuel as a constituent polymer (High moisture content) material is used. Examples of such materials include perfluorocarbons containing sulfone groups (Naphion (registered trademark, manufactured by DuPont), acyplex (registered trademark, manufactured by Asahi Kasei Corporation)), perfluorocarbons containing lipoxyl groups (Fremion). S film (made by Asahi Glass Co., Ltd.).

 In this case, there is a possibility that sufficient adhesion cannot be obtained between the solid polymer electrolyte membrane 114 and the electrode. However, in the present invention, the solid polymer electrolyte membrane 114 has the above-described uneven surface on its surface. Therefore, the adhesion between the solid polymer electrolyte membrane 114 and the electrode can be improved. This makes it possible to achieve both suppression of crossover and improvement of battery performance.

 As the fuel for the fuel cell according to the present invention, a liquid organic fuel or a hydrogen-containing gas can be used. Among them, when the liquid organic fuel is used, the cell efficiency can be improved while suppressing the crossover of the liquid fuel, and the effect of the present invention is more remarkably exhibited.

 The method for producing the solid polymer electrolyte membrane for fuel cell 114 and the fuel cell 100 in the present invention is not particularly limited. They can be made, for example, using the process shown in FIG.

 FIG. 3 is a flowchart showing a method of manufacturing a fuel cell according to the embodiment of the present invention. The method for manufacturing a fuel cell includes steps S1 to S4. Step S1 produces a solid polymer electrolyte membrane. Step S2 roughens the surface of the solid polymer electrolyte membrane. Step S3 forms a catalyst electrode. Step S 4 joins the solid polymer electrolyte membrane and the catalyst electrode. Hereinafter, each step will be described in detail.

 Step S1 will be described.

 The solid polymer electrolyte membrane 114 in the present invention can be produced by employing an appropriate method according to the material to be used. For example, when the solid polymer electrolyte membrane 114 is made of an organic polymer material, it can be obtained as follows. First, a liquid is prepared by dissolving or dispersing an organic polymer material in a solvent (step S11). Next, it is cast on a releasable sheet of polytetrafluoroethylene or the like and dried (step S12). Then, the dried solid polymer electrolyte membrane is peeled off from the peeling sheet (step S13).

 Here, by using a substance having a concavo-convex structure on the surface of the peelable sheet, it is possible to obtain a membrane having a concavo-convex structure required on the surface of the dried solid polymer electrolyte membrane 114.

Furthermore, the cast solid polymer electrolyte membrane solution or dispersion may be brought into contact with an upper part with a peelable sheet or the like having a concavo-convex structure before drying before drying. A film having the desired uneven structure can be obtained. The peelable sheet or the like used in the above method can have, for example, an arithmetic mean height (Ra) of the contour curve of preferably 0.5 nm or more, more preferably 1 nm or more. Ra can be preferably 100 nm or less, more preferably 50 nm or less. Thereby, favorable irregularities are provided on the surface of the solid polymer electrolyte membrane 114.

 The uneven surface of the release sheet may have, for example, an average length (RSm) of a contour curve element of the uneven surface of 0.5 nm or more, preferably 1 nm or more. Further, RSm can be lOO Onm or less, preferably 100 nm or less. As a result, preferable irregularities are provided on the surface of the solid polymer electrolyte membrane 114.

 Step S2 will be described.

In the production of the solid polymer electrolyte membrane 114 according to the present invention, as a method for producing the solid polymer electrolyte membrane 114 having a smooth surface by the above-described casting method, and then forming an uneven structure on the surface, for example, a solid polymer electrolyte membrane One method is to rub the surface of 114 with another substance. As a substance to be rubbed, for example, a material such as a fiber, a bundle of fibers, and a cloth can be used. The thickness of the fiber of the material to be rubbed can be, for example, 0.5 nm or more and 1 m or less. Force rubbing, for example, it can be from 1 10 k gZ cm ^2. In this case, the surface can be activated by removing the atoms on the surface by roughening the surface with fibers.

 Another method is to irradiate the surface of the polymer electrolyte membrane 114 with ions. The ion to be irradiated is, for example, argon ion. For example, in a vacuum of 10-2 Torr or less, low-angle irradiation with an acceleration voltage of 50 to 200 V (acceleration distance of 10 cm) and an incident angle of 1 to 45 degrees is performed. be able to. In this case, by irradiating the surface with ions, atoms on the surface can be removed and the state of the surface can be activated.

Further, as another method for forming a concavo-convex structure on the surface of the solid polymer electrolyte membrane 114, there is a method of performing oxygen treatment. For example, a plasma oxygen asher can be used. The plasma irradiation conditions are appropriately selected according to the degree of unevenness. For example, in a vacuum of 1 Torr or less, an RF plasma with an applied power of 100 W or more and 500 W or less (electrode area for plasma 100 cm ² ) is applied. Irradiation for up to 20 minutes provides a suitable uneven structure. In this case, the surface state can be activated by removing the surface atoms by roughening the surface with RF plasma.

 Step S3 will be described.

The catalyst of the fuel electrode 102 and the oxidizer electrode 108 can be supported on the carbon particles by a generally used impregnation method. Next, the carbon supporting the catalyst The particles and the solid polymer electrolyte are dispersed in a solvent to make a paste-like liquid (Step S31). Then, this is applied to a substrate and dried to obtain a fuel electrode 102 and an oxidizer electrode 108 (step S32). Here, the particle size of the carbon particles is, for example, 0.01 to 0.1 zm. The particle size of the catalyst particles is, for example, l nm to l Onm. The particle size of the solid polymer electrolyte particles is, for example, 0.05 to liim. The carbon particles and the solid polymer electrolyte particles are used, for example, in a weight ratio of 2: 1 to 40: 1. The weight ratio of water to solute in the cast is, for example, about 1: 2 to 10: 1. The method of applying the base to the substrate is not particularly limited, and for example, methods such as brush coating, spray coating, and screen printing can be used. The paste is applied to a thickness of about 1 zm to 2 mm. After the paste is applied, heating is performed at a heating temperature and for a heating time according to the fluororesin to be used, and a fuel electrode or an oxidizer electrode is produced. The heating temperature and the heating time are appropriately selected depending on the material used, and for example, the heating temperature can be 100 ° C to 250 ° C, and the heating time can be 30 seconds to 30 minutes.

 Step S4 will be described.

 The solid polymer electrolyte membrane 114 having the unevenness on the surface prepared as described above is sandwiched between the fuel electrode 102 and the oxidant electrode 108, and hot pressed to form a catalyst electrode-solid polymer electrolyte membrane assembly. obtain. At this time, the surfaces of both electrodes where the catalyst is provided are in contact with the solid polymer electrolyte membrane. The hot pressing conditions are selected according to the material. However, when the solid polymer electrolyte membrane 114 and the solid polymer electrolyte on the electrode surface are composed of an organic polymer having a softening point or a glass transition, these high molecular weight polymers are used. Above the softening temperature or glass transition temperature. Specifically, for example, the temperature is 100 to 250 ° C., the pressure is 1 to; L is 00 kgZcm2, and the time is 10 to 300 seconds.

 Hereinafter, a solid polymer electrolyte fuel cell using the solid polymer electrolyte membrane of the present invention and a method for producing the same will be specifically described with reference to examples, but the present invention is not limited thereto.

 [Example 1]

 In this example, a sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) film was produced, and the surface-modified one was used as a solid polymer electrolyte membrane. In other words, sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) is dissolved in isopropanol, and a plurality of membranes with a size of 10 cm X 1 O cm and a thickness of 5 O / m are prepared by casting. did.

Next, a nylon-based organic fiber having a thickness of 300 to 500 nm was rubbed on both sides of the film to provide irregularities. Unevenness of multiple solid polymer electrolyte membranes thus obtained As a result, the arithmetic mean height (Ra) of the contour curve of the film surface was in the range of lnm to 100nm. The average length (RSm) of the contour curve element on the film surface was in the range of 1 nm to 100 nm.

となった。 As the solid polymer electrolyte in the catalyst electrode, a 5 wt% naphion solution manufactured by Aldrich Chemical Co., Ltd. in which the solid polymer electrolyte was dispersed in an alcohol solution was used. The catalyst used was a catalyst-supporting carbon fine particle in which 50% by weight of platinum having a particle diameter of 3 to 5 nm was supported on carbon fine particles (Denka Black; manufactured by Denki Kagaku). The solid polymer electrolyte dispersion and the catalyst-supporting carbon fine particles were mixed at a weight ratio of 1: 2, and dispersed at 50 ° C. for 3 hours with an ultrasonic disperser to form a paste. This paste is applied by screen printing on carbon paper (TGP-H-120 made by Toray Rene Earth Co., Ltd.) to be used as a gas diffusion layer, and then heated and dried at 100 ° C to produce a solid polymer electrolyte-catalyst composite electrode. did. The amount of platinum on the obtained electrode surface is 0.1 to 0.1.

It became.

 Next, the composite electrode was heated on both sides of the sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) membrane described above at a temperature of 100 to 150 ° C and a pressure of 10 to 50 kgZcm2. Pressing was performed to produce a catalyst electrode-solid polymer electrolyte membrane assembly. At this time, two types of bonding were achieved by using a surface-treated film and an untreated film as described above as the sulfonated poly (4-phenoxybenzoyl_1,4-phenylene) film. The body was made.

 10 samples of each of these conjugates were immersed in a 10 vZv% methanol aqueous solution for 24 hours, and dried at 100. As a result of performing a peeling test using a tape on the obtained sample, the catalyst electrode peeled off from the solid polymer electrolyte membrane in all untreated membranes, but did not peel off when the surface-treated membrane was used. It was confirmed that the surface treatment significantly increased the bonding strength between the solid polymer electrolyte membrane and the catalyst electrode.

 Next, each of the catalyst electrode-solid polymer electrolyte membrane assembly prepared above was set in a fuel cell single cell measuring device, and a single cell for characteristic evaluation was prepared. In this cell,

A 10 vZv% methanol aqueous solution and oxygen gas were supplied, and the current-voltage characteristics at 1 atm and room temperature were measured. Here, the supply amounts of the aqueous methanol solution and the oxygen gas are 2 cc / min and 30 cc / min, respectively. As a result, the battery voltage at a current density of 100 mAZcm2 when the untreated membrane was used was about 35 OmV, but the battery voltage was as high as about 420 mV when the surface-treated membrane was used. Output was obtained. From this, it was confirmed that the above-mentioned surface treatment suppressed a decrease in output due to an increase in resistance at the joint surface between the solid polymer electrolyte membrane and the catalyst electrode.

[Example 2] After preparing a plurality of sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) films by the casting method in the same manner as in Example 1, the surface of the film was subjected to surface modification by irradiating argon ions to irradiate the surface. Was given. When the degree of unevenness of the solid polymer electrolyte membranes thus obtained was evaluated, the arithmetic mean height (Ra) of the contour curve on the membrane surface was in the range of 1 nm to 10 nm. In addition, the average length (RSm) of the contour curve element on the film surface ranges from l nm to 1 O nm.

 Here, argon ions were irradiated for 10 minutes in a vacuum of 10-4 Torr at an acceleration voltage of 50 V and an incident angle of 20 degrees. Further, in this example, a solid polymer electrolyte membrane Nafion 112 manufactured by DuPont, which is conventionally used for a solid polymer electrolyte membrane, was also used for comparison.

 A solid polymer electrolyte-catalyst composite electrode and a catalyst electrode-solid polymer electrolyte membrane assembly were produced in the same manner as in Example 1. In this example, the sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) membranes, which are solid polymer electrolyte membranes, were treated in the same manner as in Example 1. , Two types of conjugates were prepared. Further, in this example, a catalyst electrode-solid polymer electrolyte membrane assembly using a solid polymer electrolyte membrane made of DuPont's Naphion 112 as a solid polymer electrolyte membrane was also prepared, and the above two types of sulfonated poly (4-1) were prepared. The characteristics were compared with those using a phenoxybenzoyl (1,4-phenylene) film.

 Each of these 10 samples was immersed in a 10 vZv% methanol aqueous solution for 24 hours and then dried at 100 ° C. A peel test was performed on the obtained sample using a tape. As a result, all the bonded samples using the sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) film without surface treatment had a solid catalyst electrode. All of the bonded samples using the sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) membrane that had been peeled off from the polymer electrolyte membrane but surface-treated by argon irradiation were not peeled off. It was confirmed that the surface treatment significantly increased the bonding strength between the polymer electrolyte membrane and the catalyst electrode.

Next, each of the catalyst electrode-solid polymer electrolyte membrane assembly prepared above was set in a fuel cell single cell measuring device, and a single cell for characteristic evaluation was prepared. A 30 v / v% methanol aqueous solution and oxygen gas were supplied to this cell, and the current-voltage characteristics at 1 atm and room temperature were measured. Here, the supply amounts of the aqueous methanol solution and the oxygen gas are 2 cc / in and 30 cc / min, respectively. As a result, the battery voltage at a current density of 100 mAZcm2 was about 35 OmV when the untreated membrane was used, but the battery voltage was about 44 OmV when the above-mentioned membrane was used. High output was obtained. On the other hand, the battery voltage of a cell using a solid polymer electrolyte membrane as a conventional naph ion 112 was about 30 OmV. Less than From the above, the catalyst electrode-solid polymer electrolyte membrane assembly obtained by the present invention is

It was found that the crossover that occurs at high methanol concentration was suppressed as compared with the case where the polymer electrolyte membrane was used. Furthermore, by performing the above-described treatment on the surface of the solid polymer electrolyte membrane, it is possible to suppress a decrease in output due to an increase in resistance at the junction surface between the solid polymer electrolyte membrane and the catalyst electrode, and to improve the output of the fuel cell. Was confirmed.

 [Example 3]

 In the same manner as in Examples 1 and 2, a plurality of sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) films were prepared by the cast method, and the modified surface was used as a solid polymer electrolyte membrane. Was. Both surfaces of the thin film were subjected to an oxygen plasma asher treatment by irradiating a 400 W RF plasma for 10 minutes in an oxygen atmosphere of 0.1 T rr to provide irregularities. When the degree of unevenness of the plurality of solid polymer electrolyte membranes thus obtained was evaluated, the arithmetic average height (R a) of the contour curve of the membrane surface was in the range of 1 nm to 10 nm. The average length (R Sm) of the contour curve element on the film surface was in the range of 1 nm to 10 nm.

 A solid polymer electrolyte-catalyst composite electrode and a catalyst electrode-solid polymer electrolyte membrane assembly were produced in the same manner as in Examples 1 and 2. In this example, the sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) membrane, which is a solid polymer electrolyte membrane, was used in the same manner as in Example 1. Using these, two types of joined bodies were produced.

 Each 10 samples of these conjugates was immersed in a 10 V ZV% aqueous solution of methanol for 24 hours and then dried at 100 ° C. As a result of performing a peeling test using a tape on the obtained sample, all of the bonded samples using the sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) membrane without surface treatment had a catalytic electrode. All of the bonded samples using the sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) membrane that was peeled off from the solid polymer electrolyte membrane but surface-treated with an oxygen plasma asher were peeled off. However, it was confirmed that the surface treatment significantly increased the bonding strength between the solid polymer electrolyte membrane and the catalyst electrode. Next, each of the catalyst electrode-solid polymer electrolyte membrane assembly prepared above was set in a fuel cell single cell measuring device, and a single cell for characteristic evaluation was prepared. A 50 vZv% methanol aqueous solution and oxygen gas were supplied to the cell, and the current-voltage characteristics at 1 atm and room temperature were measured. Here, the supply amounts of the methanol aqueous solution and the oxygen gas are 2 cc / min and 30 cc / min, respectively. As a result, the battery voltage at a current density of 100 mAZ cm 2 when using the untreated surface film was about 35 OmV, but when using the above-mentioned surface-treated film. Means the battery voltage is 40

Since a high output of about 0 mV was obtained, solid polymer It was confirmed that the output reduction due to the increase in resistance at the junction surface between the decomposed membrane and the catalyst electrode was suppressed, the crossover caused by the high methanol concentration did not occur, and the output of the fuel cell was improved.

 In the above embodiments, a naphthion solution manufactured by Aldrich Chemical Company was used as the solid polymer electrolyte, but the solid polymer electrolyte is not limited to the above embodiments. From the above examples, it has been clarified that the battery characteristics are significantly improved by the present invention. That is, in the embodiment according to the present invention, by forming an uneven surface on the solid polymer electrolyte membrane, the adhesion at the interface between the catalyst electrode surface and the solid polymer electrolyte membrane is increased, thereby improving battery characteristics and battery reliability. Was able to improve. Furthermore, even when the methanol concentration in the fuel was high, it was possible to suppress the methanol crossover while maintaining good hydrogen ion conductivity on the catalyst electrode surface.

 As described above, according to the present invention, since the solid polymer electrolyte membrane having the uneven surface is used, good adhesion at the interface with the catalyst electrode can be obtained. For this reason, the adhesion at the interface between the catalyst electrode surface and the solid polymer electrolyte membrane can be enhanced, and the battery characteristics and battery reliability can be improved. In addition, crossover of organic liquid fuel can be suppressed while maintaining good hydrogen ion conductivity and organic liquid fuel permeability on the surface of the catalyst electrode.

Claims

The scope of the claims 1. a solid polymer electrolyte membrane formed of a first solid polymer electrolyte, wherein the solid polymer electrolyte membrane has an uneven surface,  A catalyst electrode joined to the uneven surface;  A fuel cell comprising: 2. In the fuel cell according to claim 1,  The catalyst electrode,  A catalyst layer,  A base layer holding the catalyst layer;  With  The catalyst layer,  A catalyst substance,  Second solid polymer electrolyte and  Including  The catalyst layer and the uneven surface are joined  Fuel cell. 3. In the fuel cell according to claim 2,  The arithmetic mean height (R a) of the contour curve on the uneven surface has a value of 0.5 nm ≤ Ra ≤ 100 nm, and the Ra is JIS-B 060 1-200 1 ( IS 0428 7-1 9 9 7)  Fuel cell. 4. In the fuel cell according to claim 3,  The average length (RSm) of the contour curve element on the uneven surface has a value of 0.5 nm ≦ R Sm ≦ 100 nm, and the RSm is JIS—B 0 6 0 1—2 0 0 1 (I S04 2 87-1 9 9 7)  Fuel cell. 5. In the fuel cell according to claim 3 or 4,  The second solid polymer electrolyte comprises a polymer compound or a derivative thereof constituting the first solid polymer electrolyte, The polymer compound and its derivative have a water content lower than a reference water content set in advance so as to suppress crossover. Fuel cell. 6. The fuel cell according to claim 5,  The polymer compound contains at least one of sulfonated poly (4-phenoxybenzoyl_1,4-phenylene) and alkylsulfonated polybenzoimidazole.  Fuel cell. 7. In the fuel cell according to claim 3 or 4,  The water content of the second solid polymer electrolyte is higher than the water content of the first solid polymer electrolyte.  Fuel cell. 8. The fuel cell according to claim 7,  The first solid polymer electrolyte includes at least one of sulfonated poly (4-phenoxybenzoic),  The second solid polymer electrolyte contains at least one of a sulfone group-containing perfluorocarbon and a sulfoxyl group-containing perfluorocarbon.  Fuel cell. 9. (a) providing a solid polymer electrolyte membrane;  (b) roughening at least one surface of the solid polymer electrolyte membrane.  A method for producing a solid polymer electrolyte membrane for a fuel cell. 10. In the method for producing a solid polymer electrolyte membrane for a fuel cell according to claim 9,  The step (b) includes:  (b 1) a step of rubbing a fiber on at least one surface of the solid polymer electrolyte membrane  A method for producing a solid polymer electrolyte membrane for a fuel cell. 11. In the method for producing a solid polymer electrolyte membrane for a fuel cell according to claim 9, The step (b) includes: (b 2) ion irradiation is provided on at least one surface of the solid polymer electrolyte membrane  A method for producing a solid polymer electrolyte membrane for a fuel cell. 12. In the method for producing a solid polymer electrolyte membrane for a fuel cell according to claim 9,  The step (b) includes:  (b3) performing a plasma treatment on at least one surface of the solid polymer electrolyte membrane;  Have  A method for producing a solid polymer electrolyte membrane for a fuel cell. 13. The method for producing a solid polymer electrolyte membrane for a fuel cell according to any one of claims 9 to 12,  Arithmetic mean height of contour curve of uneven surface on the surface of the solid polymer electrolyte membrane (Ra) has a value of 0.5 nm ≤ Ra ≤ 100 nm, and the Ra is defined by JIS-B0601-2001 (IS04287-1997).  A method for producing a solid polymer electrolyte membrane for a fuel cell. 14. The method for producing a solid polymer electrolyte membrane for a fuel cell according to claim 13,  The average length (RSm) of the contour curve element of the uneven surface on the surface of the solid polymer electrolyte membrane has a value of 0.5 nm ≤ RSm ≤ 1000 nm, and the RSm is defined by JI SB 0601 -2001 (IS 04287-1997). A method for producing a solid polymer electrolyte membrane for a fuel cell. 15. (c) roughening the surface of the solid polymer electrolyte membrane formed of the first solid polymer electrolyte;  (d) preparing a catalyst electrode including a catalyst substance and a second solid polymer electrolyte;  (e) joining the catalyst electrode to the surface of the solid polymer electrolyte membrane.  A method for manufacturing a fuel cell. 16. The method for manufacturing a fuel cell according to claim 15, The step (d) includes:  (d1) a step of applying a coating solution on a substrate to form a catalyst layer, wherein the coating solution comprises conductive particles carrying the catalyst substance, and particles containing the second solid polymer electrolyte. Containing  The step (e) includes:  (e l) contacting the surface of the solid polymer electrolyte membrane with the surface of the catalyst electrode;  (e 2) pressing the solid polymer electrolyte membrane and the catalyst electrode.  A method for manufacturing a fuel cell. 17.The method for producing a fuel cell according to claim 15, wherein the second solid polymer electrolyte is a polymer compound or a derivative thereof constituting the first solid polymer electrolyte. Consisting of  The polymer compound and its derivative have a water content lower than a reference water content set in advance so as to suppress crossover.  A method for manufacturing a fuel cell. 18. The method of manufacturing a fuel cell according to claim 17,  The polymer compound contains at least one of sulfonated poly (4-phenoxybenzoyl-1,4-phenylene) and alkylsulfonated polybenzoimidazole.  A method for manufacturing a fuel cell. 19. In the fuel cell according to claim 15 or 16,  The second moisture content of the second solid polymer electrolyte is higher than the first moisture content of the first solid polymer electrolyte.  A method for manufacturing a fuel cell. 20. The method of manufacturing a fuel cell according to claim 7,  The first solid polymer electrolyte contains at least one of sulfonated poly (4-phenoxybenzoyl 1,4-phenylene) and alkyl sulfonated polybenzoimidazole,  The second solid polymer electrolyte contains at least one of a sulfone group-containing perfluorocarbon and a sulfoxyl group-containing perfluorocarbon.  A method for manufacturing a fuel cell.