JP2014212074A - Electrolyte membrane-electrode structure with resin frame for fuel cell and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which an electrolyte membrane-electrode structure with a resin frame can be produced simply and reliably, workability and productivity can be improved, and further an end structure of an electrolyte membrane-electrode structure can be produced easily and accurately.SOLUTION: A method for producing an electrolyte membrane-electrode structure 10 with a resin frame includes the steps of: embedding an outer periphery 18e of a solid polymer electrolyte membrane 18 into an inner periphery 24a of a resin frame member 24; and accommodating a cathode electrode 20 and an anode electrode 22 into the inner periphery 24a of the resin frame member 24 to be integrated while the cathode electrode and the anode electrode are brought into contact with both surfaces 18a, 18b of the solid polymer electrolyte membrane 18.

Description

  The present invention provides an electrolyte with a resin frame for a fuel cell, comprising an electrolyte membrane / electrode structure in which electrodes are disposed on both sides of a solid polymer electrolyte membrane, and a resin frame member that circulates around the outer periphery of the solid polymer electrolyte membrane. The present invention relates to a membrane / electrode structure and a manufacturing method thereof.

  In general, a polymer electrolyte fuel cell employs a polymer electrolyte membrane made of a polymer ion exchange membrane. This fuel cell comprises an electrolyte membrane / electrode structure in which an anode electrode and a cathode electrode each comprising a catalyst layer (electrode catalyst layer) and a gas diffusion layer (porous carbon) are disposed on both sides of a solid polymer electrolyte membrane ( MEA) is sandwiched between separators. A predetermined number of the fuel cells are stacked and used, for example, as an in-vehicle fuel cell stack.

  In this type of electrolyte membrane / electrode structure, at least one of the gas diffusion layers may be set to have a smaller surface area than the solid polymer electrolyte membrane. At that time, in order to reduce the amount of the relatively expensive solid polymer electrolyte membrane used, and to protect the solid polymer electrolyte membrane having a thin film shape and low strength, an MEA with a frame incorporating a resin frame member is adopted. ing.

  For example, a fuel cell disclosed in Patent Document 1 is known. As shown in FIG. 19, this fuel cell includes an electrolyte membrane 2 in which a pair of catalyst layers 1 are formed, and a pair of electrode base materials 3 and 4 disposed so as to face each other with the electrolyte membrane 2 interposed therebetween. The seal part 6 disposed on the side of the electrolyte membrane 2 and the side of the electrode bases 3 and 4 is filled in the seal part 6 and the electrode bases 3 and 4. A resin member 7 for bonding the electrode bases 3 and 4 is provided. Further, the electrolyte membrane 2 on which the catalyst layer 1 is formed and the electrode bases 3 and 4 are joined only by adhesion with the resin member 7 at a site outside the end of the catalyst layer 1.

JP 2006-252858 A

  However, the above-mentioned Patent Document 1 has a problem that the manufacturing operation of the fuel cell becomes complicated and the fuel cell cannot be manufactured efficiently. This makes it difficult to improve fuel cell productivity.

  The present invention solves this type of problem, and can easily and reliably produce an electrolyte membrane / electrode structure with a resin frame, and can improve workability and productivity. An object of the present invention is to provide an electrolyte membrane / electrode structure with a resin frame for a fuel cell, and a method for producing the same, which can easily and accurately manufacture the end structure of the electrolyte membrane / electrode structure.

  The present invention provides an electrolyte with a resin frame for a fuel cell, comprising an electrolyte membrane / electrode structure in which electrodes are disposed on both sides of a solid polymer electrolyte membrane, and a resin frame member that circulates around the outer periphery of the solid polymer electrolyte membrane. The present invention relates to a membrane / electrode structure and a manufacturing method thereof.

  In this manufacturing method, the outer periphery of the solid polymer electrolyte membrane is embedded in the inner periphery of the resin frame member, each electrode is accommodated in the inner periphery of the resin frame member, and the both sides of the solid polymer electrolyte membrane are provided. And a step of integrating them in a contact state.

  In this production method, the integration is preferably performed using a hot press, an adhesive, or an ion conductive resin.

  Furthermore, in this production method, it is preferable that at least one of the electrodes is provided with an intermediate layer having ion conductivity on the surface in contact with the solid polymer electrolyte membrane.

  Furthermore, in the electrolyte membrane / electrode structure with a resin frame, the outer periphery of the solid polymer electrolyte membrane is embedded in the inner periphery of the resin frame member, and the electrode has a catalyst layer and a gas diffusion layer, and at least one of them. The electrode is provided with an intermediate layer made of an ion conductive component on the surface in contact with the solid polymer electrolyte membrane.

  In the present invention, electrodes are disposed on both surfaces of a solid polymer electrolyte membrane, and the outer dimension of one of the electrodes is smaller than the outer dimension of the solid polymer electrolyte membrane and the outer dimension of the other electrode. A step-shaped electrolyte membrane / electrode structure set to be the same as the outer dimensions of the solid polymer electrolyte membrane, and a resin frame member having an L-shaped cross section around the outer periphery of the solid polymer electrolyte membrane. The present invention relates to an electrolyte membrane / electrode structure with a resin frame for a fuel cell.

  In this electrolyte membrane-attached electrolyte membrane / electrode structure, the outer peripheral surface of the solid polymer electrolyte membrane extending outward from the outer periphery of one of the electrodes is the inner peripheral surface of the thin portion protruding inward of the resin frame member. At least one of the electrodes is provided with an intermediate layer made of an ion conductive component on a surface that contacts the solid polymer electrolyte membrane.

  Further, in the electrolyte membrane / electrode structure with a resin frame, the intermediate layer preferably contains a substance having the same ionic conductivity as that of the solid polymer electrolyte membrane.

  According to the present invention, the outer periphery of the solid polymer electrolyte membrane is embedded or arranged in the inner periphery (surface) of the resin frame member. For this reason, an electrode is brought into contact with both surfaces of the solid polymer electrolyte membrane and integrated, whereby an electrolyte membrane / electrode structure with a resin frame is manufactured. Therefore, the electrolyte membrane / electrode structure with a resin frame can be easily and reliably manufactured, and workability and productivity can be improved.

It is a principal part disassembled perspective explanatory view of the polymer electrolyte fuel cell in which the resin membrane-attached electrolyte membrane / electrode structure according to the first embodiment of the present invention is incorporated. FIG. 2 is a sectional view of the fuel cell taken along line II-II in FIG. 1. 3A is an explanatory diagram when the solid polymer electrolyte membrane and the resin frame member are integrated, FIG. 3B is an explanatory diagram of another integration process, and FIG. 3C is still another integration process. It is explanatory drawing of. It is explanatory drawing at the time of providing an electrode catalyst layer in an intermediate | middle layer. It is explanatory drawing at the time of adhere | attaching the said electrode catalyst layer and a gas diffusion layer. It is explanatory drawing at the time of manufacturing a cathode electrode and an anode electrode. It is explanatory drawing at the time of integrating with the said cathode electrode and the said anode electrode in the said solid polymer electrolyte membrane. It is principal part cross-sectional explanatory drawing of the polymer electrolyte fuel cell in which the electrolyte membrane-electrode structure with a resin frame concerning the 2nd Embodiment of this invention is integrated. It is explanatory drawing of the method to manufacture the said electrolyte membrane-electrode structure with a resin frame. It is principal part cross-sectional explanatory drawing of the polymer electrolyte fuel cell in which the electrolyte membrane-electrode structure with a resin frame concerning the 3rd Embodiment of this invention is integrated. It is explanatory drawing of the method to manufacture the said electrolyte membrane-electrode structure with a resin frame. It is principal part cross-sectional explanatory drawing of the polymer electrolyte fuel cell in which the electrolyte membrane-electrode structure with a resin frame concerning the 4th Embodiment of this invention is integrated. It is explanatory drawing of the method to manufacture the said electrolyte membrane-electrode structure with a resin frame. It is principal part cross-sectional explanatory drawing of the polymer electrolyte fuel cell in which the electrolyte membrane and electrode structure with a resin frame concerning the 5th Embodiment of this invention is integrated. It is explanatory drawing of the method to manufacture the said electrolyte membrane-electrode structure with a resin frame. It is principal part sectional explanatory drawing of the polymer electrolyte fuel cell in which the electrolyte membrane and electrode structure with a resin frame concerning the 6th Embodiment of this invention is integrated. It is explanatory drawing of the method to manufacture the said electrolyte membrane-electrode structure with a resin frame. It is principal part cross-sectional explanatory drawing of the polymer electrolyte fuel cell in which the electrolyte membrane and electrode structure with a resin frame concerning the 7th Embodiment of this invention is integrated. 2 is a cross-sectional explanatory view of a fuel cell disclosed in Patent Document 1. FIG.

  As shown in FIGS. 1 and 2, an electrolyte membrane / electrode structure 10 with a resin frame according to the first embodiment of the present invention is incorporated into a solid polymer fuel cell 12. For example, an in-vehicle fuel cell stack is configured by stacking a plurality of fuel cells 12 in the direction of arrow A.

  In the fuel cell 12, the electrolyte membrane / electrode structure 10 with a resin frame is sandwiched between the first separator 14 and the second separator 16. The first separator 14 and the second separator 16 are made of, for example, a steel plate, a stainless steel plate, an aluminum plate, a plated steel plate, a metal thin plate whose surface is subjected to anticorrosion treatment, a carbon member, or the like. .

  As shown in FIG. 2, the electrolyte membrane / electrode structure 10 with a resin frame includes an electrolyte membrane / electrode structure 10a. The electrolyte membrane / electrode structure 10 a includes, for example, a hydrocarbon-based solid polymer electrolyte membrane 18 and a cathode electrode 20 and an anode electrode 22 that sandwich the solid polymer electrolyte membrane 18. As the hydrocarbon electrolyte membrane, for example, a material obtained by sulfonating an engineering plastic polymer such as polyether ether ketone, polyether sulfone, polyether imide, polyphenylene ether or the like is used.

  The cathode electrode 20 and the anode electrode 22 are set to have the same planar dimension and have a smaller planar dimension than the solid polymer electrolyte membrane 18. The cathode electrode 20 is disposed on one surface 18 a of the solid polymer electrolyte membrane 18, and the anode electrode 22 is disposed on the other surface 18 b of the solid polymer electrolyte membrane 18.

  The cathode electrode 20 includes a first electrode catalyst layer 20a and a first gas diffusion layer 20b stacked on the first electrode catalyst layer 20a. The cathode electrode 20 is provided with a first intermediate layer 23a made of an ion conductive component on the surface in contact with the surface 18a of the solid polymer electrolyte membrane 18, that is, on the first electrode catalyst layer 20a. The first intermediate layer 23a is made of, for example, a fluorine electrolyte membrane. The first intermediate layer 23 a may be composed of a hydrocarbon-based electrolyte membrane, similarly to the solid polymer electrolyte membrane 18, and may be the same component as the solid polymer electrolyte membrane 18. The 1st intermediate | middle layer 23a should just be a layer which contains a fluorine-type ion conductive component or a hydrocarbon type ion conductive component as a main component.

  The anode electrode 22 includes a second electrode catalyst layer 22a and a second gas diffusion layer 22b stacked on the second electrode catalyst layer 22a. The anode electrode 22 is provided with a second intermediate layer 23b made of an ion conductive component on the surface in contact with the surface 18b of the solid polymer electrolyte membrane 18, that is, on the second electrode catalyst layer 22a. The second intermediate layer 23b is made of, for example, a fluorine electrolyte membrane. Note that the second intermediate layer 23 b may be composed of a hydrocarbon-based electrolyte membrane, like the solid polymer electrolyte membrane 18.

  The first electrode catalyst layer 20a and the second electrode catalyst layer 22a form, for example, catalyst particles in which platinum particles are supported on carbon black (if the catalyst has excellent power generation performance, it is not limited to platinum particles), and ions A polymer paste is used as a conductive binder, and a catalyst paste prepared by uniformly mixing the catalyst particles in a solution of the polymer electrolyte is printed on the first intermediate layer 23a and the second intermediate layer 23b. It is configured by coating or transferring. Alternatively, the first electrode catalyst layer 20a and the second electrode catalyst layer 22a may be configured by printing, applying, or transferring to the first gas diffusion layer 20b and the second gas diffusion layer 22b.

  The first gas diffusion layer 20b and the second gas diffusion layer 22b are formed, for example, by applying a base layer containing carbon black and PTFE (polytetrafluoroethylene) particles to the catalyst layer side of the carbon paper. The underlayer has the same surface dimensions as the carbon paper. In addition, what is necessary is just to provide a base layer as needed. The planar dimension of the first gas diffusion layer 20b is set to the same dimension as the planar dimension of the second gas diffusion layer 22b.

  As shown in FIGS. 1 and 2, the electrolyte membrane / electrode structure 10 with a resin frame includes a resin frame member 24, and an outer periphery 18 e of a solid polymer electrolyte membrane 18 is disposed on an inner periphery 24 a of the resin frame member 24. And the anode electrode 22 and the cathode electrode 20 are joined.

  The resin frame member 24 includes, for example, PES (polyethersulfone), LCP (liquid crystal polymer), PPS (polyphenylene sulfide), PEEK (polyetheretherketone), PFA (tetrafluoroethylene / perfluoroalkylvinylether copolymer). ), Etc., or two or more kinds of polymer alloys, general-purpose engineering plastics such as PP (polypropylene), or two or more kinds of polymer alloys.

  The inner periphery 24 a of the resin frame member 24 and the outer periphery of the cathode electrode 20 and the outer periphery of the anode electrode 22 are bonded by, for example, an adhesive layer 26. As the adhesive layer 26, for example, a thermosetting adhesive such as a liquid fluoroelastomer is used.

  As shown in FIG. 1, one end edge of the fuel cell 12 in the arrow B direction (horizontal direction in FIG. 1) communicates with each other in the arrow A direction, which is the stacking direction, and contains an oxidant gas, for example, oxygen An oxidant gas inlet communication hole 30a for supplying gas, a cooling medium inlet communication hole 32a for supplying a cooling medium, and a fuel gas outlet communication hole 34b for discharging a fuel gas, for example, a hydrogen-containing gas, Arranged in the direction of arrow C (vertical direction).

  The other end edge of the fuel cell 12 in the direction of arrow B communicates with each other in the direction of arrow A, a fuel gas inlet communication hole 34a for supplying fuel gas, and a cooling medium outlet communication hole for discharging the cooling medium. 32b and an oxidant gas outlet communication hole 30b for discharging the oxidant gas are arranged in the direction of arrow C.

  An oxidant gas flow path 36 communicating with the oxidant gas inlet communication hole 30a and the oxidant gas outlet communication hole 30b is provided on the surface 16a of the second separator 16 facing the electrolyte membrane / electrode structure 10 with a resin frame. .

  A fuel gas flow path 38 communicating with the fuel gas inlet communication hole 34a and the fuel gas outlet communication hole 34b is formed on the surface 14a of the first separator 14 facing the electrolyte membrane / electrode structure 10 with a resin frame. A cooling medium flow path 40 communicating with the cooling medium inlet communication hole 32a and the cooling medium outlet communication hole 32b is formed between the surface 14b of the first separator 14 and the surface 16b of the second separator 16 adjacent to each other. .

  As shown in FIG. 2, the oxidant gas passage 36 and the fuel gas passage 38 are provided from the power generation surface to a portion facing the resin frame member 24. This is to ensure drainage. The channel groove of the oxidant gas channel 36 and the channel groove of the fuel gas channel 38 are opposed to the boundary part between the resin frame member 24 and the cathode electrode 20 and the boundary part between the resin frame member 24 and the anode electrode 22. Provided.

  As shown in FIGS. 1 and 2, the first seal member 42 is integrated with the surfaces 14 a and 14 b of the first separator 14 around the outer peripheral end of the first separator 14. The second seal member 44 is integrated with the surfaces 16 a and 16 b of the second separator 16 around the outer peripheral end portion of the second separator 16.

  As shown in FIG. 2, the first seal member 42 includes a first convex seal 42 a that contacts the resin frame member 24 constituting the electrolyte membrane / electrode structure 10 with a resin frame, and a second seal of the second separator 16. And a second convex seal 42b in contact with the member 44. The first convex seal 42a is located on the outer side of the outer periphery of the solid polymer electrolyte membrane 18 with respect to the stacking direction (arrow A direction), that is, located at a site where only the resin frame member 24 exists. In contact with the resin frame member 24. This is to prevent the solid polymer electrolyte membrane 18 from being loaded.

  The second seal member 44 constitutes a flat seal in which the surface that contacts the second convex seal 42b has a flat shape along the separator surface. Instead of the second convex seal 42b, the second seal member 44 may be provided with a convex seal (not shown).

  The first and second sealing members 42 and 44 include, for example, EPDM, NBR, fluorine rubber, silicone rubber, fluorosilicone rubber, butyl rubber, natural rubber, styrene rubber, chloroprene or acrylic rubber, a cushioning material, Alternatively, an elastic seal member such as a packing material is used.

  Next, a manufacturing method according to the first embodiment for manufacturing the electrolyte membrane / electrode structure 10 with a resin frame will be described below.

  First, as shown in FIG. 3A, the outer periphery 18e of the solid polymer electrolyte membrane 18 is embedded and the resin frame member 24 is injection-molded, for example. For this reason, the solid polymer electrolyte membrane 18 and the resin frame member 24 are integrated. As shown in FIG. 3B, the solid polymer electrolyte membrane 18 is sandwiched and welded between the two resin frame constituent portions 24P1 and 24P2, and the solid polymer electrolyte membrane 18 and the resin frame member 24 are integrated. Also good. Further, as shown in FIG. 3C, the solid polymer electrolyte membrane 18 is sandwiched and welded between the two resin frame constituent portions 24P3 and 24P4, and the solid polymer electrolyte membrane 18 and the resin frame member 24 are integrated. Also good. The resin frame constituent parts 24P2, 24P3 and 24P4 are preferably provided with recesses for disposing the solid polymer electrolyte membrane 18.

  Next, as shown in FIG. 4, the first electrode catalyst layer 20a of the cathode electrode 20 and the second electrode catalyst layer 22a of the anode electrode 22 are manufactured. Specifically, a binder solution is put into a mixture of a catalyst and a solvent, and an electrode sheet obtained by applying electrode ink mixed to a predetermined ink viscosity to a PET sheet made of a PET film by screen printing is formed. The sheet is stacked on the first intermediate layer 23a and the second intermediate layer 23b and hot pressed. Then, the first electrode catalyst layer 20a and the second electrode catalyst layer 22a are formed on the first intermediate layer 23a and the second intermediate layer 23b by peeling the PET sheet.

  Furthermore, in the manufacturing process of the first gas diffusion layer 20b and the second gas diffusion layer 22b, a slurry in which a mixture containing carbon black and PTFE (polytetrafluoroethylene) particles is uniformly dispersed in ethylene glycol is formed. The slurry is applied to carbon paper and dried to produce a first gas diffusion layer 20b and a second gas diffusion layer 22b composed of the carbon paper and a base layer (see FIG. 5). As another example, after the first electrode catalyst layer 20a and the second electrode catalyst layer 22a are provided in the first gas diffusion layer 20b and the second gas diffusion layer 22b, the first intermediate layer 23a and the second intermediate layer are provided. 23b may be integrated.

  Therefore, the first electrode catalyst layer 20a and the first gas diffusion layer 20b are laminated together and bonded by an adhesive or thermocompression bonding, whereby the cathode electrode 20 is manufactured (see FIG. 6). At that time, since the first intermediate layer 23a, the first electrode catalyst layer 20a, and the first gas diffusion layer 20b are set to the same plane dimensions, each is prepared in advance to have a large plane dimension and is bonded by a Thomson blade or the like after bonding. You may punch out to a desired size. In addition, you may produce the 1st intermediate | middle layer 23a, the 1st electrode catalyst layer 20a, and the 1st gas diffusion layer 20b in roll shape. For this reason, the cathode electrode 20 can be manufactured easily and with high accuracy. The same applies to the anode electrode 22 described below.

  In the anode electrode 22, the second electrode catalyst layer 22a and the second gas diffusion layer 22b are integrally laminated and bonded by an adhesive or thermocompression bonding, whereby the anode electrode 22 is manufactured.

  Thereafter, as shown in FIG. 7, the cathode electrode 20 is accommodated in the inner periphery 24 a of the resin frame member 24 and is disposed with the first intermediate layer 23 a in contact with the surface 18 a of the solid polymer electrolyte membrane 18. The The anode electrode 22 is accommodated in the inner periphery 24 a of the resin frame member 24, and is disposed with the second intermediate layer 23 b in contact with the surface 18 b of the solid polymer electrolyte membrane 18. The first intermediate layer 23a, the solid polymer electrolyte membrane 18, and the second intermediate layer 23b are bonded by an ion conductive resin or an adhesive. For this reason, the electrolyte membrane and electrode structure 10 with a resin frame is manufactured.

  Note that the bonding method may employ, for example, thermocompression bonding (hot pressing) in addition to the above-described ion conductive resin and adhesive. Further, the inner periphery 24 a of the resin frame member 24 can be adhered to the outer periphery of the cathode electrode 20 and the outer periphery of the anode electrode 22 by applying an adhesive. Further, the resin frame member 24 may be slightly melted, and the inner periphery 24a and the outer periphery of the cathode electrode 20 and the outer periphery of the anode electrode 22 may be bonded together by welding.

  As shown in FIG. 2, the resin membrane-attached electrolyte membrane / electrode structure 10 is sandwiched between the first separator 14 and the second separator 16. The first separator 14 contacts the resin frame member 24 and applies a load to the electrolyte membrane / electrode structure 10 with a resin frame together with the second separator 16. Furthermore, a predetermined number of fuel cells 12 are stacked to form a fuel cell stack, and a clamping load is applied between end plates (not shown).

  The operation of the fuel cell 12 configured as described above will be described below.

  First, as shown in FIG. 1, an oxidant gas such as an oxygen-containing gas is supplied to the oxidant gas inlet communication hole 30a, and a fuel gas such as a hydrogen-containing gas is supplied to the fuel gas inlet communication hole 34a. Further, a cooling medium such as pure water, ethylene glycol, or oil is supplied to the cooling medium inlet communication hole 32a.

  For this reason, the oxidant gas is introduced into the oxidant gas flow path 36 of the second separator 16 from the oxidant gas inlet communication hole 30a, and moves in the direction of arrow B to the cathode electrode 20 of the electrolyte membrane / electrode structure 10a. Supplied. On the other hand, the fuel gas is introduced into the fuel gas flow path 38 of the first separator 14 from the fuel gas inlet communication hole 34a. The fuel gas moves in the direction of arrow B along the fuel gas flow path 38 and is supplied to the anode electrode 22 of the electrolyte membrane / electrode structure 10a.

  Therefore, in each electrolyte membrane / electrode structure 10a, the oxidant gas supplied to the cathode electrode 20 and the fuel gas supplied to the anode electrode 22 are consumed by an electrochemical reaction in the electrode catalyst layer to generate power. Done.

  Next, the oxidant gas consumed by being supplied to the cathode electrode 20 is discharged in the direction of arrow A along the oxidant gas outlet communication hole 30b. Similarly, the fuel gas consumed by being supplied to the anode electrode 22 is discharged in the direction of arrow A along the fuel gas outlet communication hole 34b.

  The cooling medium supplied to the cooling medium inlet communication hole 32a is introduced into the cooling medium flow path 40 between the first separator 14 and the second separator 16, and then flows in the direction of arrow B. The cooling medium is discharged from the cooling medium outlet communication hole 32b after the electrolyte membrane / electrode structure 10a is cooled.

  In this case, in the first embodiment, as shown in FIG. 7, the outer periphery 18 e of the solid polymer electrolyte membrane 18 is embedded and integrated in the inner periphery 24 a of the resin frame member 24. On the other hand, the cathode electrode 20 and the anode electrode 22 are respectively integrated. That is, three units are configured in advance.

  Therefore, the resin membrane-attached electrolyte membrane / electrode structure 10 is manufactured simply by bringing the cathode electrode 20 and the anode electrode 22 into contact with and integrated with both surfaces 18a, 18b of the solid polymer electrolyte membrane 18. Therefore, it is possible to easily and surely manufacture the electrolyte membrane / electrode structure 10 with a resin frame, and it is possible to improve the workability and productivity. Furthermore, it can suppress that the position of the outer peripheral part of the anode electrode 22 and the outer peripheral part of the cathode electrode 20 shifts or varies.

  Moreover, in the first embodiment, the solid polymer electrolyte membrane 18 is composed of a hydrocarbon-based electrolyte membrane, and high heat resistance and mechanical strength can be obtained. Can be suppressed gracefully. On the other hand, the 1st intermediate | middle layer 23a and the 2nd intermediate | middle layer 23b are comprised by the fluorine-type electrolyte membrane with high ion conductivity. Thereby, the first intermediate layer 23a and the second intermediate layer 23b are securely bonded to the solid polymer electrolyte membrane 18, and the high-performance cathode electrode 20 and anode electrode 22 can be manufactured.

  The first intermediate layer 23a on the cathode electrode 20 side and the second intermediate layer 23b on the anode electrode 22 side may be set to different materials. For example, the first intermediate layer 23a may be composed of a hydrocarbon-based electrolyte membrane, while the second intermediate layer 23b may be composed of a fluorine-based electrolyte membrane. For this reason, the electrolyte membrane / electrode structure 10a can be freely designed, and it is possible to optimally set the moisture content and the resistance to active substances, peroxide substances, and the like.

  FIG. 8 is a cross-sectional explanatory view of a main part of a polymer electrolyte fuel cell 62 incorporating a resin frame-attached electrolyte membrane / electrode structure 60 according to a second embodiment of the present invention. In addition, the same referential mark is attached | subjected to the component same as the electrolyte membrane and electrode structure 10 with a resin frame and fuel cell 12 which concern on 1st Embodiment, and the detailed description is abbreviate | omitted. Similarly, in the third and subsequent embodiments described below, detailed description thereof is omitted.

  The electrolyte membrane / electrode structure 60 with a resin frame includes an electrolyte membrane / electrode structure 60a. The cathode electrode 20 constituting the electrolyte membrane / electrode structure 60a includes a first electrode catalyst layer 20a, a first gas diffusion layer 20b, and an intermediate layer 64 in contact with the surface 18a of the solid polymer electrolyte membrane 18. The intermediate layer 64 is made of an ion conductive component, and is composed of, for example, a fluorine electrolyte membrane or a hydrocarbon electrolyte membrane.

  The anode electrode 22 constituting the electrolyte membrane / electrode structure 60a includes the second electrode catalyst layer 22a and the second gas diffusion layer 22b, and no intermediate layer is provided. In addition, while providing the intermediate layer in the anode electrode 22, the intermediate layer 64 of the cathode electrode 20 can be made unnecessary.

  Next, a manufacturing method according to the second embodiment for manufacturing the electrolyte membrane / electrode structure 60 with a resin frame will be described below.

  As shown in FIG. 9, the solid polymer electrolyte membrane 18 and the resin frame member 24 are integrated. On the other hand, in the cathode electrode 20, as in the first embodiment, after the first electrode catalyst layer 20 a is formed on the intermediate layer 64 by coating or transfer, the first gas diffusion layer 20 b is formed on the first electrode catalyst layer 20 a. Are bonded by an adhesive or thermocompression bonding. In the anode electrode 22, the second electrode catalyst layer 22 a is applied or transferred to the second gas diffusion layer 22 b to manufacture the anode electrode 22.

  The anode electrode 22 and the cathode electrode 20 can be formed in desired dimensions by punching with a Thomson blade or the like.

  The cathode electrode 20 is disposed with the intermediate layer 64 in contact with the surface 18a of the solid polymer electrolyte membrane 18, and the anode electrode 22 has the second electrode catalyst layer 22a disposed on the solid polymer electrolyte membrane 18. It arrange | positions in contact with the surface 18b.

  The intermediate layer 64, the solid polymer electrolyte membrane 18, and the second electrode catalyst layer 22 a are integrally bonded by an ion conductive resin, an adhesive, thermocompression bonding, or the like, and the electrolyte membrane / electrode structure 60 with a resin frame is manufactured. The Thus, in the second embodiment, the same effect as in the first and second embodiments can be obtained.

  As shown in FIG. 10, an electrolyte membrane / electrode structure 70 with a resin frame according to a third embodiment of the present invention is incorporated into a solid polymer fuel cell 72.

  The electrolyte membrane / electrode structure 70 with a resin frame includes an electrolyte membrane / electrode structure 70a. The electrolyte membrane / electrode structure 70a includes a cathode electrode 20 and an anode electrode 22 that sandwich the solid polymer electrolyte membrane 18, and the cathode electrode 20 is set to have a smaller planar dimension than the anode electrode 22, and is so-called A step MEA is formed.

  The cathode electrode 20 includes a first intermediate layer 74a, a first electrode catalyst layer 20a, and a first gas diffusion layer 20b, which are set to have the same planar dimensions. The anode electrode 22 includes a second intermediate layer 74b, a second electrode catalyst layer 22a, and a second gas diffusion layer 22b, which are set to have the same planar dimensions.

  The first intermediate layer 74a and the second intermediate layer 74b are made of, for example, a fluorine-based electrolyte membrane. The first intermediate layer 74a and the second intermediate layer 74b may be made of different materials. For example, the first intermediate layer 74a is made of a hydrocarbon-based electrolyte membrane, while the second intermediate layer is made of 74b may be composed of a fluorine-based electrolyte membrane.

  An outer periphery 18 e of the solid polymer electrolyte membrane 18 is embedded in the resin frame member 76. The resin frame member 76 has a first inner periphery 76a and a second inner periphery 76b via a step portion, and the first inner periphery 76a protrudes inward from the second inner periphery 76b.

  The outer circumference of the cathode electrode 20 is joined to the first inner circumference 76a by, for example, an adhesive, and the outer circumference of the anode electrode 22 is joined to the second inner circumference 76b, for example, by an adhesive. .

  As shown in FIG. 11, the resin membrane-attached electrolyte membrane / electrode structure 70 is integrated by embedding an outer periphery 18 e of the solid polymer electrolyte membrane 18 in a resin frame member 76. As in the first embodiment, the cathode electrode 20 and the anode electrode 22 are integrated in advance. The cathode electrode 20 brings the first intermediate layer 74a into contact with the surface 18a of the solid polymer electrolyte membrane 18, while the anode electrode 22 causes the second intermediate layer 74b to contact the surface 18b of the solid polymer electrolyte membrane 18. Make contact.

  These three parts are bonded by a conductive resin, an adhesive, thermocompression bonding, or the like, and an electrolyte membrane / electrode structure 70 with a resin frame is manufactured.

  As described above, the third embodiment can be applied easily and reliably to the step MEA in which the cathode electrode 20 is set to have a smaller planar dimension than the anode electrode 22, and the first embodiment described above. The same effect can be obtained. The anode electrode 22 can be set to have a smaller planar dimension than the cathode electrode 20, thereby obtaining the same effect as that of the third embodiment.

  As shown in FIG. 12, an electrolyte membrane / electrode structure 80 with a resin frame according to the fourth embodiment of the present invention is incorporated in a polymer electrolyte fuel cell 82.

  The electrolyte membrane / electrode structure 80 with a resin frame includes an electrolyte membrane / electrode structure 80a. The electrolyte membrane / electrode structure 80a includes, for example, a fluorine-based solid polymer electrolyte membrane 84, and a cathode electrode 20 and an anode electrode 22 that sandwich the solid polymer electrolyte membrane 84. The cathode electrode 20 and the anode electrode 22 are set to have the same planar dimension and have a smaller planar dimension than the solid polymer electrolyte membrane 84.

  The cathode electrode 20 includes a first intermediate layer 86a, a first electrode catalyst layer 20a, and a first gas diffusion layer 20b. The anode electrode 22 includes a second intermediate layer 86b, a second electrode catalyst layer 22a, and a second gas diffusion layer 22b. The first intermediate layer 86a and the second intermediate layer 86b are composed of, for example, a hydrocarbon electrolyte membrane.

  As shown in FIG. 13, first, the resin frame member 24 is integrated by embedding the outer periphery 84 e of the solid polymer electrolyte membrane 84 in the resin membrane-attached electrolyte membrane / electrode structure 80.

  Next, in the cathode electrode 20, after the first electrode catalyst layer 20a is applied to the first intermediate layer 86a, it is bonded to the first gas diffusion layer 20b by an adhesive or thermocompression bonding. On the other hand, the anode electrode 22 is similarly bonded to the second gas diffusion layer 22b after the second electrode catalyst layer 22a is applied to the second intermediate layer 86b.

  The first intermediate layer 86a is disposed on the surface 84a of the solid polymer electrolyte membrane 84, and the second intermediate layer 86b is disposed on the surface 84b of the solid polymer electrolyte membrane 84, and these are integrated. The

  Thus, in the fourth embodiment, the solid polymer electrolyte membrane 84 is composed of a fluorine-based electrolyte membrane with high ion conductivity, and the first intermediate layer 86a and the second intermediate layer 86b It is composed of a hydrocarbon electrolyte membrane with high mechanical strength. Therefore, the resin frame-attached electrolyte membrane / electrode structure 80 has an effect of ensuring high durability performance.

  As shown in FIG. 14, an electrolyte membrane / electrode structure 90 with a resin frame according to a fifth embodiment of the present invention is incorporated into a solid polymer fuel cell 92.

  The electrolyte membrane / electrode structure 90 with a resin frame includes an electrolyte membrane / electrode structure 90a. The cathode electrode 20 constituting the electrolyte membrane / electrode structure 90a includes an intermediate layer 94 joined to the surface 84a of the fluorine-based solid polymer electrolyte membrane 84. The intermediate layer 94 includes the first electrode catalyst layer 20a and the first electrode layer 90a. A gas diffusion layer 20b is laminated. The intermediate layer 94 is composed of, for example, a hydrocarbon electrolyte membrane. The anode electrode 22 includes a second electrode catalyst layer 22a and a second gas diffusion layer 22b without using an intermediate layer.

  In such a configuration, as shown in FIG. 15, the solid polymer electrolyte membrane 84 and the resin frame member 24 are integrated.

  In the cathode electrode 20, as in the fourth embodiment, the intermediate layer 94, the first electrode catalyst layer 20a, and the first gas diffusion layer 20b are integrated, and in the anode electrode 22, the second gas diffusion layer 22b is integrated. The second electrode catalyst layer 22a is applied and integrated.

  The cathode electrode 20 and the anode electrode 22 are in contact with the surfaces 84a and 84b of the solid polymer electrolyte membrane 84, and these are integrated by an adhesive, an ion conductive resin, hot press or the like. Thereby, in 5th Embodiment, the effect similar to said 1st-4th embodiment is acquired.

  As shown in FIG. 16, an electrolyte membrane / electrode structure 100 with a resin frame according to a sixth embodiment of the present invention is incorporated in a polymer electrolyte fuel cell 102.

  The electrolyte membrane / electrode structure 100 with a resin frame includes an electrolyte membrane / electrode structure 100a. The electrolyte membrane / electrode structure 100 a constitutes a so-called step MEA in which the cathode electrode 20 is set to have a smaller planar dimension than the anode electrode 22.

  The cathode electrode 20 has a first intermediate layer 104a bonded to the surface 84a of the fluorine-based solid polymer electrolyte membrane 84, while the anode electrode 22 is bonded to the surface 84b of the solid polymer electrolyte membrane 84. The intermediate layer 104b is included.

  The first intermediate layer 104a and the second intermediate layer 104b are composed of, for example, a hydrocarbon electrolyte membrane. The outer periphery 84 e of the solid polymer electrolyte membrane 84 is embedded in the resin frame member 106.

  The resin frame member 106 has a first inner periphery 106 a joined to the outer periphery of the cathode electrode 20 and a second inner periphery 106 b joined to the outer periphery of the anode electrode 22.

  As shown in FIG. 17, the resin membrane-attached electrolyte membrane / electrode structure 100 is integrated by embedding the outer periphery 84 e of the solid polymer electrolyte membrane 84 in the resin frame member 106. In the cathode electrode 20, the first intermediate layer 104a, the first electrode catalyst layer 20a, and the first gas diffusion layer 20b are integrated, and in the anode electrode 22, the second intermediate layer 104b, the second electrode catalyst layer 22a, and the first gas diffusion layer 20b are integrated. The two gas diffusion layers 22b are integrated. Thereafter, the first intermediate layer 104a is disposed on the surface 84a, and the second intermediate layer 104b is disposed on the surface 84b, and these are integrated.

  Thus, in the sixth embodiment, the same effect as in the first to fifth embodiments can be obtained. In the sixth embodiment, the cathode electrode 20 is set to have a smaller plane size than the anode electrode 22. Conversely, the cathode electrode 20 has a larger plane size than the anode electrode 22. May be set.

  As shown in FIG. 18, an electrolyte membrane / electrode structure 110 with a resin frame according to a seventh embodiment of the present invention is incorporated in a polymer electrolyte fuel cell 111. The same components as those of the resin frame-attached electrolyte membrane / electrode structure 100 according to the sixth embodiment are denoted by the same reference numerals, and detailed description thereof is omitted.

  The electrolyte membrane / electrode structure 110 with a resin frame includes an electrolyte membrane / electrode structure 110a which is a so-called step MEA. The electrolyte membrane / electrode structure 110 a includes a solid polymer electrolyte membrane 112, and an outer dimension smaller than the outer dimension of the solid polymer electrolyte membrane 112 is set on the surface 112 a of the solid polymer electrolyte membrane 112. A cathode electrode 20 is provided. On the surface 112 b of the solid polymer electrolyte membrane 112, an anode electrode 22 set to the same outer dimensions as the outer dimensions of the solid polymer electrolyte membrane 112 is provided.

  The electrolyte membrane / electrode structure 110 with a resin frame includes a resin frame member 114, and the resin frame member 114 has an L-shaped cross section in the thickness direction (arrow A direction). The resin frame member 114 is provided with a thin portion 116 protruding inward, and an outer peripheral edge portion of the surface 112 a of the solid polymer electrolyte membrane 112 is disposed on the inner peripheral surface 116 a of the thin portion 116.

  After only the solid polymer electrolyte membrane 112 is integrally joined to the resin frame member 114, the cathode electrode 20 and the anode electrode 22 are integrated on both sides of the solid polymer electrolyte membrane 112. In the resin frame member 114, the first inner periphery 114a, which is the tip of the thin portion 116, is joined to the outer periphery of the cathode electrode 20, and the second inner periphery 114b located outward from the first inner periphery 114a is connected to the anode. The outer periphery of the electrode 22 is joined.

  In the seventh embodiment configured as described above, the same effects as those of the first to sixth embodiments can be obtained. Note that the second intermediate layer 104b may be provided only on the anode electrode 22 side without providing the first intermediate layer 104a on the cathode electrode 20 side. Further, the first intermediate layer 104a may be provided only on the cathode electrode 20 side, while the second intermediate layer 104b may not be provided on the anode electrode 22 side. Further, the cathode electrode 20 and the anode electrode 22 may be installed opposite to the resin frame member 114. The same applies to the first to sixth embodiments.

10, 60, 70, 80, 90, 100, 110 ... Electrolyte membrane / electrode structure with resin frame 10a, 60a, 70a, 80a, 90a, 100a ... Electrolyte membrane / electrode structure 12, 62, 72, 82, 92 , 102, 111 ... fuel cells 14, 16 ... separators 18, 84, 112 ... solid polymer electrolyte membranes 18a, 18b, 84a, 84b ... surfaces 18e, 84e ... outer periphery 20 ... cathode electrodes 20a, 22a ... electrode catalyst layer 20b, 22b ... Gas diffusion layer 22 ... Anode electrodes 23a, 23b, 64, 74a, 74b, 86a, 86b, 94, 104a, 104b ... Intermediate layers 24, 76, 106, 114 ... Resin frame members 24a, 76a, 76b, 106a, 106b, 114a, 114b ... inner circumference 26 ... adhesive layer 30a ... oxidant gas inlet communication hole 30b ... oxidant gas outlet communication hole 2a ... Cooling medium inlet communication hole 32b ... Cooling medium outlet communication hole 34a ... Fuel gas inlet communication hole 34b ... Fuel gas outlet communication hole 36 ... Oxidant gas flow path 38 ... Fuel gas flow path 40 ... Cooling medium flow paths 42, 44 ... Seal member 116 ... Thin part

Claims (6)

An electrolyte membrane / electrode structure with a resin frame for a fuel cell, comprising: an electrolyte membrane / electrode structure in which electrodes are disposed on both sides of the solid polymer electrolyte membrane; and a resin frame member that goes around the outer periphery of the solid polymer electrolyte membrane A method for manufacturing a body,
Embedding the outer periphery of the solid polymer electrolyte membrane in the inner periphery of the resin frame member;
A step of accommodating each electrode in the inner periphery of the resin frame member and integrating the electrodes in contact with both surfaces of the solid polymer electrolyte membrane; and
A method for producing an electrolyte membrane / electrode structure with a resin frame for a fuel cell, comprising:   2. The method of manufacturing an electrolyte membrane / electrode structure with a resin frame for a fuel cell according to claim 1, wherein the integration is performed using a hot press, an adhesive, or an ion conductive resin.   3. The manufacturing method according to claim 1, wherein at least one of the electrodes is provided with an intermediate layer having ion conductivity on a surface in contact with the solid polymer electrolyte membrane. Manufacturing method of electrolyte membrane / electrode structure. An electrolyte membrane / electrode structure with a resin frame for a fuel cell, comprising: an electrolyte membrane / electrode structure in which electrodes are disposed on both sides of the solid polymer electrolyte membrane; and a resin frame member that goes around the outer periphery of the solid polymer electrolyte membrane Body,
The outer periphery of the solid polymer electrolyte membrane is embedded in the inner periphery of the resin frame member,
The electrode has a catalyst layer and a gas diffusion layer,
An electrolyte membrane / electrode structure with a resin frame for a fuel cell, characterized in that at least one of the electrodes is provided with an intermediate layer made of an ion conductive component on a surface in contact with the solid polymer electrolyte membrane. Electrodes are disposed on both surfaces of the solid polymer electrolyte membrane, the outer dimension of one of the electrodes is smaller than the outer dimension of the solid polymer electrolyte membrane, and the outer dimension of the other electrode is the solid polymer electrolyte. A fuel cell resin comprising: a step-like electrolyte membrane / electrode structure set to have the same outer dimension as the membrane; and a resin frame member having a L-shaped cross section around the outer periphery of the solid polymer electrolyte membrane An electrolyte membrane / electrode structure with a frame,
The outer peripheral surface of the solid polymer electrolyte membrane extending outward from the outer periphery of one of the electrodes is disposed on the inner peripheral surface of the thin portion protruding inward of the resin frame member,
At least one of the electrodes is provided with an electrolyte membrane / electrode structure with a resin frame for a fuel cell, wherein an intermediate layer made of an ion conductive component is provided on a surface in contact with the solid polymer electrolyte membrane.   6. An electrolyte membrane / electrode structure with a resin frame for a fuel cell according to claim 4 or 5, wherein the intermediate layer contains a substance having the same ionic conductivity as that of the solid polymer electrolyte membrane. Electrolyte membrane / electrode structure with resin frame.

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