JP2007213997A - Solid polyelectrolyte membrane electrode assembly and solid polymer electrolyte fuel cell utilizing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cell capable of achieving a low cost and a long life, and a solid polymer electrolyte fuel cell utilizing the same. <P>SOLUTION: The cell 10 has a fuel electrode membrane 12 arranged on one face side of a solid polymer electrolyte membrane 11 and an oxidation electrode membrane 13 arranged on the other face side. The solid polymer electrolyte membrane is provided with a fluorine system solid polymer electrolyte membrane 11a which is installed on oxidation electrode membrane 13 side and has a fluorine system resin as a skeleton and has a proton conductive group, a hydrocarbon system solid polymer electrolyte membrane 11b which is installed on the fuel electrode membrane 12 side and has as a skeleton a hydrocarbon system resin having a benzene ring as a main chain and carbon and hydrogen as a main component and has the proton conductive group, and a fluorine system solid polymer electrolyte membrane 11c which is installed between the fuel electrode membrane 12 and the hydrocarbon system solid polymer electrolyte membrane 11b and has a fluorine system resin as a skeleton and has the proton conductive group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a solid polymer electrolyte membrane electrode assembly and a solid polymer electrolyte fuel cell using the same.

A solid polymer electrolyte fuel cell is a solid polymer in which a solid polymer electrolyte membrane made of a fluororesin having a proton (H ⁺ ) conductive group such as a sulfonic acid group is sandwiched between a fuel electrode membrane and an oxide electrode membrane. A stack is formed by stacking a plurality of electrolyte membrane electrode assemblies (cells), and a fuel gas containing hydrogen (H ₂ ) is supplied to the fuel electrode membrane side, and an oxidizing gas containing oxygen (O ₂ ) is oxidized. Electric power can be obtained by supplying it to the electrode membrane side and allowing hydrogen and oxygen to react electrochemically through the solid polymer electrolyte membrane.

JP 2005-317362 A

By the way, in the conventional solid polymer electrolyte fuel cell as described above, side reaction substances such as hydrogen peroxide (H ₂ O ₂ ) are likely to be generated in the vicinity of the electrode film during the above-described reaction, Part of the fuel gas supplied to the fuel electrode membrane permeates the solid polymer electrolyte membrane and reaches the oxide electrode membrane side, or part of the oxidizing gas supplied to the oxygen electrode membrane side It was easy to cause a so-called crossover that permeated the electrolyte membrane and reached the fuel electrode membrane side. If the hydrogen peroxide thus generated and the gas flowing in due to crossover coexist in the vicinity of the catalyst in the electrode film, hydroxy radicals (.OH) are generated from the hydrogen peroxide. That was newly revealed. In particular, it has been newly clarified that the hydroxy radicals are more likely to be generated on the peripheral edge side of the electrode film than on the center side, and more easily on the oxide electrode film side than on the fuel electrode film side.

  When the hydroxy radical is generated in this manner, it reacts with the solid polymer electrolyte membrane and gradually degrades and gradually degrades the solid polymer electrolyte membrane, and the solid polymer electrolyte membrane has a short life. End up.

  For this reason, various studies have been made on the development of materials for solid polymer electrolyte membranes that are unlikely to cause crossover and have high radical resistance. However, they have become very expensive and presently have difficulties in practical use. It was.

  In view of the above, an object of the present invention is to provide a solid polymer electrolyte membrane electrode assembly capable of extending the life at low cost and a solid polymer electrolyte fuel cell using the same.

  The solid polymer electrolyte membrane electrode assembly according to the first invention for solving the above-mentioned problem is provided with a fuel electrode membrane on one side of the solid polymer electrolyte membrane and oxidized on the other side. A solid polymer electrolyte membrane / electrode assembly in which an electrode membrane is disposed, wherein the solid polymer electrolyte membrane is provided on the oxidation electrode membrane side and has a fluorine resin as a skeleton and a proton conductive group A solid polymer electrolyte membrane, and a hydrocarbon-based resin having a benzene ring in the main chain and having a main composition of carbon and hydrogen provided on the fuel electrode membrane side and having a proton conductive group And a hydrocarbon-based solid polymer electrolyte membrane.

  A solid polymer electrolyte membrane electrode assembly according to a second invention is the first invention, wherein the solid polymer electrolyte membrane is between the fuel electrode membrane and the hydrocarbon-based solid polymer electrolyte membrane. And a fluorine-containing solid polymer electrolyte membrane having a proton-conductive group and a fluorine-based resin as a skeleton.

  A solid polymer electrolyte membrane electrode assembly according to a third aspect of the invention is the first or second aspect of the invention, wherein the fluorine-based solid polymer electrolyte membrane of the solid polymer electrolyte membrane is a peripheral edge of the electrode membrane. It is arranged only in the vicinity of the end.

  A solid polymer electrolyte membrane electrode assembly according to a fourth aspect of the present invention is the fluorinated solid polymer electrolyte membrane of the solid polymer electrolyte membrane according to any one of the first to third aspects of the invention. Resin is polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoroethylene copolymer (FEP), tetrafluoroethylene-hexafluoropropylene copolymer (PFEP), poly (trifluoroethylene chloride) (PCTFE), trifluoride chloride Ethylene-ethylene copolymer (ECTFE), tetrafluoroethylene-perfluorodioxole copolymer (TFE / PD At least one of), or, characterized in that it is a derivative thereof.

  The solid polymer electrolyte membrane / electrode assembly according to a fifth aspect of the present invention is the solid polymer electrolyte membrane / electrode assembly according to any one of the first to fourth aspects, wherein the carbonization of the hydrocarbon-based solid polymer electrolyte membrane of the solid polymer electrolyte membrane is performed. Hydrogen-based resins are polybenzoxazole (PBO), polybenzothiazole (PBT), polybenzimidazole (PBI), polyphenylene oxide (PPO), polyphenylene sulfoxide (PPSO), polyphenylene sulfide (PPS), polyphenylene sulfide sulfone (PPS / SO2), polyparaphenylene (PPP), polysulfone (PSU), polyphenylenesulfone (PPSU), polyethersulfone (PES), polyetherethersulfone (PEES), polyetherketone (PEK), polyetheretherketone (PE) K), polyether ketone ketone (PEKK), polyimide (PI), polyetherimide (PEI), polystyrene (PS), polyphenylene ether (PPE), polyaryl ether sulfone (PAS), or It is a derivative.

  A solid polymer electrolyte membrane electrode assembly according to a sixth aspect of the present invention provides the solid polymer electrolyte membrane electrode assembly according to any one of the first to fourth aspects of the invention, wherein the carbonization of the hydrocarbon-based solid polymer electrolyte membrane of the solid polymer electrolyte membrane is performed. The hydrogen resin is a benzene ring in the main chain of at least one of a vinyl polymer, a diene polymer, an ether polymer, a condensed ester polymer, a condensed amide polymer, or a derivative thereof. It is characterized by having.

  A solid polymer electrolyte fuel cell according to the seventh aspect of the invention for solving the above-described problem is a plurality of solid polymer electrolyte membrane electrode assemblies according to any of the first to sixth aspects of the invention. It is characterized by having a stacked stack.

  According to the solid polymer electrolyte membrane electrode assembly and the solid polymer electrolyte fuel cell using the same according to the present invention, the solid polymer electrolyte membrane is a fluorine-based solid polymer electrolyte membrane provided on the oxidation electrode membrane side. And a hydrocarbon solid polymer electrolyte membrane provided on the fuel electrode membrane side, the crossover of the fuel gas and the oxidizing gas can be greatly suppressed, and the solid polymer electrolyte by radicals Deterioration of the film can be significantly suppressed, and furthermore, since the film can be manufactured at low cost, the life can be extended at low cost.

  Embodiments of a solid polymer electrolyte membrane electrode assembly and a solid polymer electrolyte fuel cell using the same according to the present invention will be described below with reference to the drawings. However, the present invention is limited to the following embodiments. is not.

[First embodiment]
A first embodiment of a solid polymer electrolyte membrane electrode assembly (hereinafter referred to as “cell”) and a solid polymer electrolyte fuel cell using the same according to the present invention will be described with reference to FIG. FIG. 1 is a schematic configuration diagram of a cell.

  As shown in FIG. 1, the cell according to this embodiment is a cell in which a fuel electrode membrane 12 is provided on one side of a solid polymer electrolyte membrane 11 and an oxide electrode membrane 13 is provided on the other side. 10, a solid polymer electrolyte membrane 11 is provided on the oxidation electrode membrane 13 side and has a fluorine-based resin as a skeleton and a proton conductive group on the fuel electrode membrane 12 side. And a hydrocarbon solid polymer electrolyte membrane 11b having a benzene ring in the main chain and having a skeleton of a hydrocarbon resin having a main composition of carbon and hydrogen and having a proton conductive group. In addition, a fluorine-based solid polymer electrolyte membrane 11c provided between the fuel electrode membrane 12 and the hydrocarbon-based solid polymer electrolyte membrane 11b and having a fluorine-based resin as a skeleton and a proton conductive group is further provided. What Ie, it is the hydrocarbon-based solid polymer electrolyte membrane 11b that is sandwiched between the fluorine-based solid polymer electrolyte membrane 11a, 11c.

The fluorinated solid polymer electrolyte membranes 11a and 11c are made of a cation exchanger polymer having a fluorinated resin as a skeleton and a proton (H ⁺ ) conductive group (for example, a sulfonic acid group (SO ₃ ⁻ )). For example, “Nafion (registered trademark)” manufactured by DuPont, “Flemion (registered trademark)” manufactured by Asahi Glass Co., Ltd., “Aciplex (registered trademark)” manufactured by Asahi Kasei Corporation, etc.) , Polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE) ), Tetrafluoroethylene-hexafluoroethylene copolymer (FEP), tetrafluoroethylene-hexafluoropropylene Among polymers (PFEP), poly (trifluoroethylene chloride) (PCTFE), trifluoroethylene chloride-ethylene copolymer (ECTFE), tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD) Or at least one of them, or a derivative thereof.

The hydrocarbon-based solid polymer electrolyte membrane 11b is composed of a hydrocarbon-based resin having a benzene ring in the main chain and mainly composed of carbon (C) and hydrogen (H) as a skeleton and a proton (H ⁺ ) A cation exchanger polymer having a conductive group (for example, sulfonic acid group (SO ₃ ⁻ ) and the like), and examples of the resin serving as a skeleton include polybenzoxazole (PBO) and polybenzothiazole (PBT). , Polybenzimidazole (PBI), polyphenylene oxide (PPO), polyphenylene sulfoxide (PPSO), polyphenylene sulfide (PPS), polyphenylene sulfide sulfone (PPS / SO2), polyparaphenylene (PPP), polysulfone (PSU), polyphenylene sulfone ( PPSU), polyethersulfone (PES), polyether -Tersulfone (PEES), Polyetherketone (PEK), Polyetheretherketone (PEEK), Polyetherketoneketone (PEKK), Polyimide (PI), Polyetherimide (PEI), Polystyrene (PS), Polyphenyleneether (PPE) , At least one of polyaryl ether sulfone (PAS) or derivatives thereof, and vinyl polymers, diene polymers, ether polymers, condensed ester polymers, condensed systems. At least one of amide type polymers (for example, polyethylene (PE), polypropylene (PP), polyvinylidene chloride (PVDC), polyether nitrile (PEN), polyacrylonitrile (PAN), polymethylpentene (TPX), ethylene -Vinyla (Lucol copolymer (EVOH), ethylene-vinyl acetate copolymer (EVA), thermoplastic urethane (TPU), cellulose triacetate (CTA), etc.), or derivatives thereof having a benzene ring in the main chain, etc. In particular, polyphenylene sulfide (PPS) or the like is very preferable in terms of cost.

  The fuel electrode membrane 12 is formed by binding a carbon powder carrying a Pt—Ru-based catalyst in a film shape with a binder made of a polymer electrolyte such as a fluorine-based cation exchanger polymer.

  The oxide electrode film 13 is formed by binding a carbon powder carrying a Pt-based catalyst in a film shape with a binder made of a polymer electrolyte such as a fluorine-based cation exchanger polymer.

  The cell 10 having such a structure is sandwiched between carbon cloth or carbon paper, which is a gas diffusion layer having gas diffusibility and conductivity, and further, a fuel gas flow path is formed on one side and oxidized on the other side. A stack is configured by stacking a plurality of layers through conductive separators in which gas flow paths are formed.

In the solid polymer electrolyte fuel cell according to the present embodiment having such a stack, a fuel gas containing hydrogen (H ₂ ) is supplied to the fuel gas flow path of each separator, and the fuel electrode of each cell 10 is supplied. Each of the gas diffusion layers is supplied to the membrane 12 through the gas diffusion layer, and an oxidizing gas containing oxygen (O ₂ ) is supplied to the oxidizing gas flow path of each separator to diffuse the gas into the oxidation electrode film 13 of each cell 10. When supplied through the layers, electricity can be taken out by hydrogen and oxygen reacting electrochemically in each cell 10.

  The spent fuel gas used for the reaction is discharged from the fuel gas flow path of each separator to the outside of the stack, and the used oxidizing gas used for the reaction is stacked from the oxidizing gas flow path of each separator. It is discharged outside.

  Here, the solid polymer electrolyte membrane 11 is a gas barrier in which the hydrocarbon solid polymer electrolyte membrane 11b is sandwiched between the fluorine solid polymer electrolyte membranes 11a and 11c, that is, having high radical resistance. The fluorinated solid polymer electrolyte membranes 11a and 11c having low properties are positioned on the electrode membranes 12 and 13 side where hydroxyl radicals are likely to be generated, and are much lower than the fluorinated solid polymer electrolyte membranes 11a and 11c. The hydrocarbon-based solid polymer electrolyte membrane 11b having low radical resistance can be used for the above-mentioned fluorine-based solid polymer, although it is costly and has a very rigid structure because it has a benzene ring in the main chain. It is interposed between the molecular electrolyte membranes 11a and 11c.

  For this reason, in the solid polymer electrolyte fuel cell according to this embodiment, even if the fuel gas is supplied to the fuel electrode membrane 12 of each cell 10 and the oxidizing gas is supplied to the oxygen electrode membrane 13 of each cell 10, Since the hydrocarbon-based solid polymer electrolyte membrane 11b having high gas barrier properties is interposed between the electrode membranes 12 and 13, the crossover of the gas can be greatly suppressed.

Further, during the above-described reaction or the like, side reaction substances such as hydrogen peroxide (H ₂ O ₂ ) are generated in the vicinity of the electrode films 12 and 13, and a slight amount of hydroxy radicals are contained in the electrode films 12 and 13. Even if it occurs in the vicinity of the catalyst, the fluorine-based solid polymer electrolyte membranes 11a and 11c having high radical resistance become the hydrocarbon-based solid polymer electrolyte membrane 11b and the electrode films 12 and 13 having low radical resistance. Since the hydrocarbon-based solid polymer electrolyte membrane 11b is laminated so as to be interposed between the two, the degradation of the hydrocarbon-based solid polymer electrolyte membrane 11b due to the radicals can be significantly suppressed.

  Furthermore, the hydrocarbon-based solid polymer electrolyte membrane 11b, which is lower in cost than the fluorine-based solid polymer electrolyte membranes 11a, 11c, is provided between the fluorine-based solid polymer electrolyte membranes 11a, 11c, thereby solid polymer electrolyte membranes. 11 can be obtained at a lower cost than in the case of a solid polymer electrolyte membrane consisting entirely of a fluorine-based solid polymer electrolyte membrane.

  Therefore, according to the cell 10 and the solid polymer electrolyte fuel cell according to the present embodiment, it is possible to extend the life at low cost.

[Second Embodiment]
A second embodiment of a cell according to the present invention and a solid polymer electrolyte fuel cell utilizing the same will be described with reference to FIG. FIG. 2 is a schematic configuration diagram of a cell. In addition, about the part similar to the case of 1st embodiment mentioned above, by using the code | symbol similar to the code | symbol used in description of 1st embodiment mentioned above, 1st embodiment mentioned above is used. The description overlapping with the description in is omitted.

  As shown in FIG. 2, the cell according to this embodiment is a cell in which a fuel electrode film 12 is disposed on one side of a solid polymer electrolyte membrane 21 and an oxide electrode film 13 is disposed on the other side. 20, a solid polymer electrolyte membrane 21 is provided on the oxidation electrode membrane 13 side, and has a fluorine resin as a skeleton and a proton conductive group, and a solid polymer electrolyte membrane 21 a on the fuel electrode membrane 12 side. A hydrocarbon solid polymer electrolyte membrane 21b having a benzene ring in the main chain and having a skeleton of a hydrocarbon resin having a main composition of carbon and hydrogen and having a proton conductive group. In addition, a fluorine-based solid polymer electrolyte membrane 21c provided between the fuel electrode membrane 12 and the hydrocarbon-based solid polymer electrolyte membrane 21b and having a fluorine-based resin as a skeleton and having a proton conductive group is further provided. And The fluorine-based solid polymer electrolyte membranes 21a and 21c are disposed only in the vicinity of the peripheral edges of the electrode films 12 and 13, that is, on both sides so as to correspond to the vicinity of the peripheral edges of the electrode films 12 and 13. On the stepped portions 21ba and 21bc of the hydrocarbon-based solid polymer electrolyte membrane 21b in which stepped portions 21ba and 21bc are respectively formed along the peripheral edge, a frame-shaped (b-shaped) fluorine-based solid polymer electrolyte membrane 21a, A solid polymer electrolyte membrane 21 provided so as to fit 21c is used.

  In the cell 20 having such a structure, for example, a fluorine-based solid polymer electrolyte membrane 21a cut out in a frame shape (b-shaped) is disposed on one surface of a flat-plate hydrocarbon solid polymer electrolyte membrane. A hydrocarbon-based solid polymer electrolyte membrane corresponding to the shape of the space portion is disposed in the space portion inside the fluorine-based solid polymer electrolyte membrane 21a having a frame shape (b-shaped), or a hydrocarbon-based After applying and drying the material slurry of the solid polymer electrolyte membrane, a fluorine-based solid polymer electrolyte membrane 21c cut out into a frame shape (b-shaped) is disposed on the other surface, and the frame shape (b-shaped) The hydrocarbon solid polymer electrolyte membrane corresponding to the shape of the space portion is disposed in the space portion inside the fluorine-based solid polymer electrolyte membrane 21c, or the material of the hydrocarbon solid polymer electrolyte membrane Apply slurry and dry Further, a frame-shaped (b-shaped) fluorine-based solid polymer electrolyte membrane is formed on the stepped portions 21ba and 21bc of the hydrocarbon-based solid polymer electrolyte membrane 21b in which grooves 21ba and 21bc are formed along the peripheral edge on both sides. The solid polymer electrolyte membrane 21 provided so as to be fitted with 21a and 21c can be easily obtained, and the electrode membranes 12 and 13 are joined to the solid polymer electrolyte membrane 21 by hot pressing, so that it can be easily manufactured. can do.

  That is, the cell 10 according to the first embodiment described above applies the solid polymer electrolyte membrane 11 provided with the fluorine-based solid polymer electrolyte membranes 11a and 11c over the entire surface of the hydrocarbon-based solid polymer electrolyte membrane 11b. However, the cell 20 according to the present embodiment includes a fluorine-based solid polymer electrolyte membrane only on a portion of the hydrocarbon-based solid polymer electrolyte membrane 21b that can be in contact with the vicinity of the peripheral edges of the electrode films 12 and 13. The solid polymer electrolyte membrane 21 provided with 21a and 21c is applied.

  In the solid polymer electrolyte fuel cell according to this embodiment provided with a stack constituted by stacking the cells 20 having such a structure in the same manner as in the first embodiment described above, Similarly to the case of the first embodiment, when the fuel gas is supplied to the fuel electrode film 12 of each cell 20 and the oxidizing gas is supplied to the oxide electrode film 13 of each cell 20, hydrogen and oxygen are supplied in each cell 20. Can react electrochemically and take out electricity.

  Here, the solid polymer electrolyte membrane 21 is a fluorine-based solid polymer electrolyte membrane 21a, 21c only on a portion of the hydrocarbon-based solid polymer electrolyte membrane 21b that can be in contact with the vicinity of the peripheral edge of the electrode films 12, 13. That is, the hydrocarbon-based solid polymer electrolyte membrane 21b that has high radical resistance but has low radical resistance compared to the hydrocarbon-based solid polymer electrolyte membrane 21b that exhibits high gas barrier properties but has low radical resistance has low gas barrier properties. The fluorine-based solid polymer electrolyte membranes 21a and 21c, which are more expensive than the membrane 21b, are provided only on the peripheral edge sides of the electrode membranes 12 and 13 where hydroxy radicals are easily generated.

  For this reason, in the solid polymer electrolyte fuel cell according to the present embodiment, fuel gas is supplied to the fuel electrode film 12 of each cell 20 and each cell 20 as in the case of the first embodiment described above. Even if the oxidizing gas is supplied to the oxygen electrode film 13, the gas-based crossover of the gas is greatly reduced because the hydrocarbon-based polymer electrolyte membrane 21b having a high gas barrier property is interposed between the electrode films 12 and 13. Can be suppressed.

Further, during the above-described reaction or the like, side reaction substances such as hydrogen peroxide (H ₂ O ₂ ) are generated in the vicinity of the electrode films 12 and 13, and a slight amount of hydroxy radicals are contained in the electrode films 12 and 13. Even if it occurs in the vicinity of the catalyst, the fluorine-based solid polymer electrolyte membranes 21a and 21c having high radical resistance are formed on the peripheral edge side of the electrode films 12 and 13 where hydroxyl radicals are likely to be generated, and carbonization having low radical resistance. Since it is located on the peripheral edge side of the hydrocarbon-based solid polymer electrolyte membrane 21b so as to be interposed between the hydrogen-based solid polymer electrolyte membrane 21b, the hydrocarbon-based solid polymer electrolyte membrane 21b due to the radicals. Can be greatly suppressed.

  Furthermore, the fluorine-based solid polymer electrolyte membranes 21a and 21c, which are more expensive than the hydrocarbon-based solid polymer electrolyte membrane 21b, are provided only on the peripheral edge side of the electrode membranes 12 and 13 where hydroxyl radicals are easily generated. Since the electrolyte membrane 21 is configured, it can be obtained at a lower cost than in the case of the first embodiment described above.

  Therefore, according to the cell 20 and the solid polymer electrolyte fuel cell according to the present embodiment, the same effects as those of the first embodiment described above can be obtained, and the first embodiment described above. The cost can be further reduced as compared with the above case.

[Other Embodiments]
In the first and second embodiments described above, the solid polymer electrolyte membranes 11a, 11c, 21a, and 21c are disposed on both sides of the hydrocarbon solid polymer electrolyte membranes 11b and 21b, respectively. Although the case of the cells 10 and 20 to which the molecular electrolyte membranes 11 and 21 are applied has been described, the hydroxy radical is more likely to be generated on the oxide electrode membrane 13 side than on the fuel electrode membrane 12 side. For example, as shown in FIGS. 3 and 4, a solid polymer electrolyte membrane 31 in which fluorine-based solid polymer electrolyte membranes 11a and 21a are disposed only on the oxidation electrode membrane 13 side of the hydrocarbon-based solid polymer electrolyte membranes 11b and 41b. , 41, that is, the cell 30 in which the fuel electrode membrane 12 is disposed on one side of the solid polymer electrolyte membranes 31, 41 and the oxide electrode membrane 13 is disposed on the other surface side. 40, the solid polymer electrolyte membranes 31 and 41 are provided on the oxide electrode membrane 13 side, have a fluorine resin as a skeleton, and have a proton conductive group, fluorine polymer solid polymer electrolyte membranes 11a and 21a, and a fuel electrode. A hydrocarbon-based solid polymer electrolyte membrane 11b provided on the membrane 12 side and having a benzene ring in the main chain and having a skeleton of a hydrocarbon-based resin having a main composition of carbon and hydrogen and having a proton conductive group , 41b can also be provided. In this case, the same effects as those of the first and second embodiments described above can be obtained, and the cost can be further reduced as compared with the cases of the first and second embodiments described above. Can do.

  In the first and second embodiments described above, the case where a stack in which a plurality of cells 10 and 20 are stacked is used for a solid polymer electrolyte fuel cell has been described. As another embodiment, for example, By supplying raw water to a stack formed by stacking a plurality of the cells 10, 20, 30, 40, and electrolyzing the raw water in the cells 10, 20, 30, 40, oxygen containing ozone and It can also be used for an ozone generator that generates hydrogen.

  The solid polymer electrolyte membrane electrode assembly according to the present invention and the solid polymer electrolyte fuel cell using the same can be used effectively in various industries because the lifetime can be extended at low cost. it can.

It is a schematic block diagram of 1st embodiment of the solid polymer electrolyte membrane electrode assembly which concerns on this invention. It is a schematic block diagram of 2nd embodiment of the solid polymer electrolyte membrane electrode assembly which concerns on this invention. It is a schematic block diagram of the other example of 1st embodiment of the solid polymer electrolyte membrane electrode assembly which concerns on this invention. It is a schematic block diagram of the other example of 2nd embodiment of the polymer electrolyte membrane electrode assembly which concerns on this invention.

Explanation of symbols

10, 20, 30, 40 Solid polymer electrolyte membrane electrode assembly (cell)
11, 21, 31, 41 Solid polymer electrolyte membrane 11a, 11c, 21a, 21c Fluorine-based solid polymer electrolyte membrane 11b, 21b, 31b, 41b Hydrocarbon-based solid polymer electrolyte membrane 21ba, 21bc Step 12 Fuel electrode membrane 13 Oxidized electrode membrane

Claims (7)

In the solid polymer electrolyte membrane electrode assembly in which the fuel electrode membrane is disposed on one side of the solid polymer electrolyte membrane and the oxide electrode membrane is disposed on the other surface side,
The solid polymer electrolyte membrane is
A fluorine-based solid polymer electrolyte membrane provided on the oxidation electrode membrane side and having a fluorine-based resin as a skeleton and having a proton conductive group;
A hydrocarbon-based solid polymer electrolyte having a benzene ring in the main chain and having a main component of carbon and hydrogen as a skeleton and a proton-conducting group provided on the fuel electrode membrane side A solid polymer electrolyte membrane electrode assembly comprising a membrane. In claim 1,
The solid polymer electrolyte membrane is
A fluorine-based solid polymer electrolyte membrane that is provided between the fuel electrode membrane and the hydrocarbon-based solid polymer electrolyte membrane and has a fluorine-based resin as a skeleton and a proton conductive group; A solid polymer electrolyte membrane electrode assembly characterized. In claim 1 or claim 2,
The solid polymer electrolyte membrane electrode assembly, wherein the fluorine-based solid polymer electrolyte membrane of the solid polymer electrolyte membrane is disposed only in the vicinity of the peripheral edge of the electrode membrane. In any one of Claims 1-3,
The fluorine resin of the fluorine-based solid polymer electrolyte membrane of the solid polymer electrolyte membrane is:
Polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE) , Tetrafluoroethylene-hexafluoroethylene copolymer (FEP), Tetrafluoroethylene-hexafluoropropylene copolymer (PFEP), Polytrifluoroethylene chloride (PCTFE), Trifluoroethylene chloride-ethylene A solid polymer electrolyte membrane / electrode assembly comprising at least one of a copolymer (ECTFE) and a tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD) or a derivative thereof . In any one of Claims 1-4,
The hydrocarbon resin of the hydrocarbon-based solid polymer electrolyte membrane of the solid polymer electrolyte membrane is:
Polybenzoxazole (PBO), polybenzothiazole (PBT), polybenzimidazole (PBI), polyphenylene oxide (PPO), polyphenylene sulfoxide (PPSO), polyphenylene sulfide (PPS), polyphenylene sulfide sulfone (PPS / SO2), polypara Phenylene (PPP), Polysulfone (PSU), Polyphenylenesulfone (PPSU), Polyethersulfone (PES), Polyetherethersulfone (PEES), Polyetherketone (PEK), Polyetheretherketone (PEEK), Polyetherketoneketone (PEKK), polyimide (PI), polyetherimide (PEI), polystyrene (PS), polyphenylene ether (PPE), polyaryl ether sulfo At least one of (PAS), or a solid polymer electrolyte membrane electrode assembly, which is a derivative thereof. In any one of Claims 1-4,
The hydrocarbon resin of the hydrocarbon-based solid polymer electrolyte membrane of the solid polymer electrolyte membrane is:
At least one of vinyl polymers, diene polymers, ether polymers, condensed ester polymers, condensed amide polymers, or derivatives thereof having a benzene ring in the main chain A solid polymer electrolyte membrane electrode assembly characterized by the above. A solid polymer electrolyte fuel cell, comprising a stack in which a plurality of the solid polymer electrolyte membrane electrode assemblies according to claim 1 are stacked.

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