WO2011096205A1 - 高分子電解質形燃料電池 - Google Patents
高分子電解質形燃料電池 Download PDFInfo
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- WO2011096205A1 WO2011096205A1 PCT/JP2011/000567 JP2011000567W WO2011096205A1 WO 2011096205 A1 WO2011096205 A1 WO 2011096205A1 JP 2011000567 W JP2011000567 W JP 2011000567W WO 2011096205 A1 WO2011096205 A1 WO 2011096205A1
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- fuel cell
- flow path
- reaction gas
- polymer electrolyte
- gas flow
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
- H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
- H01M8/0263—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant having meandering or serpentine paths
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
- H01M8/0265—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant the reactant or coolant channels having varying cross sections
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0267—Collectors; Separators, e.g. bipolar separators; Interconnectors having heating or cooling means, e.g. heaters or coolant flow channels
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to the structure of a polymer electrolyte fuel cell.
- a polymer electrolyte fuel cell (hereinafter referred to as PEFC) generates electric power and heat simultaneously by electrochemically reacting a fuel gas containing hydrogen and an oxidant gas containing oxygen such as air. is there.
- a single cell (cell) of PEFC is composed of a polymer electrolyte membrane and a pair of gas diffusion electrodes (anode and cathode), a MEA (Membrane-Electrode-Assembly), a gasket, and a conductive material. And a plate-like separator.
- the PEFC is generally formed by stacking a plurality of cells, sandwiching both ends of the stacked cells with end plates, and fastening the end plates and the cells with a fastener. For this reason, in the polymer electrolyte membrane, stress (fastening pressure) larger than the other portions is present in the vicinity of the portion that contacts the outer periphery of the catalyst layer of the gas diffusion electrode (hereinafter referred to as the outer peripheral contact portion of the polymer electrolyte membrane). Take it. In addition, by repeating the start / stop operation of PEFC, tensile stress and compressive stress are repeatedly applied to the polymer electrolyte membrane. In particular, these stresses are applied to the outer peripheral contact portion of the polymer electrolyte membrane. There is a problem that it takes a large amount and damages such as distortion and cracks easily occur.
- FIG. 21 is a schematic diagram showing a schematic configuration of a cell of a polymer electrolyte fuel cell disclosed in Patent Document 1. As shown in FIG. In FIG. 21, a part is omitted.
- the cell 200 of the polymer electrolyte fuel cell disclosed in Patent Document 1 is formed on the opposite side of the oxygen electrode catalyst layer 202C from the side on which the polymer film 201 is present or on the fuel electrode catalyst layer 203C.
- Reinforcing members 204 and 205 that can be elastically deformed are provided on the side opposite to the side on which the molecular film 201 is present so as to extend from the inside and outside of the periphery of the oxygen electrode catalyst layer 202C or the fuel electrode catalyst layer 203C.
- Patent Document 1 even if tensile stress or compressive stress is repeatedly applied to the polymer film 201 due to elastic deformation of the reinforcing members 204 and 205, the oxygen electrode boundary film portion 201W and the fuel of the polymer film 201 are used. Since it is suppressed that stress is applied to the pole boundary film portion 201W, it is described that damages such as strain and cracks are prevented from occurring in the oxygen electrode boundary film portion 201W and the fuel electrode boundary film portion 201W of the polymer film 201. Has been.
- Patent Document 1 Even the solid polymer fuel cell disclosed in Patent Document 1 still has room for improvement in that the polymer membrane is damaged and the battery performance is lowered.
- the present invention has been made in order to solve the above-mentioned problems, and a polymer electrolyte fuel cell capable of suppressing deterioration factors in a portion where the polymer electrolyte membrane is likely to deteriorate and suppressing a decrease in battery performance. And it aims at providing a separator.
- the inventors of the present invention have found the following points as a result of intensive studies to solve the above-described problems of the prior art.
- the inventors conducted a durability test of the cell 200 of the polymer electrolyte fuel cell of Patent Document 1 shown in FIG. 21 and found that the reinforcing members 204 and 205 of the polymer film 201 were seen from the thickness direction of the cell 200.
- the film thickness of the portion 201P facing (overlapping) the inner end portions 204E and 205E of the inner portions 204E and 205E was thinner than the other portions. This is because the inner end portions 204E and 205E of the reinforcing members 204 and 205 apply a strong stress to the portion 201P of the polymer membrane 201 via the oxygen electrode catalyst layer 202C and / or the fuel electrode catalyst layer 203C.
- the film thickness of 201P is thinner than the other parts, and as a result, the cross leak of the reaction gas in the part 201P increases. That is, in the cell 200 disclosed in Patent Document 1, a reactive gas cross leak occurs around the portion 201P of the polymer film 201, and the oxygen electrode catalyst layer 202C and / or the fuel electrode catalyst are generated by the cross leaked reactive gas. Hydrogen peroxide is generated on the catalyst of the layer 203C, and the polymer film 201 is attacked by radicals generated by the Fenton reaction or the like. As a result, the present inventors have found that the polymer film 201 has deteriorated, causing a decrease in battery performance.
- the inventors of the present invention have found that it is extremely effective to adopt the configuration described below to achieve the object of the present invention, and have come up with the present invention.
- a polymer electrolyte fuel cell includes a polymer electrolyte membrane, a membrane-electrode assembly having a pair of electrodes sandwiching the polymer electrolyte membrane, a plate-like separator having conductivity.
- the electrode has a catalyst layer and a gas diffusion layer, one main surface of which is in contact with the polymer electrolyte membrane, and its outer periphery is the outer periphery of the polymer electrolyte membrane as viewed from the thickness direction of the separator.
- the membrane-electrode assembly is sandwiched between a pair of separators, and the separator penetrates the main surface thereof in the thickness direction and the reactive gas supply manifold hole and the reactive gas.
- a discharge manifold hole is formed, and one main surface in contact with the electrode is connected to the reaction gas discharge manifold hole and a groove-shaped first connection channel connected to the reaction gas supply manifold hole. And at least one main surface of the separator and the gas diffusion layer has one end communicating with the first connection flow path and the other end connected to the second connection flow path.
- a plurality of groove-like reaction gas flow paths communicating with the passage are formed, and when the plurality of reaction gas flow paths are traced from the upstream end to the downstream end when viewed from the thickness direction of the separator, the peripheral edges of the electrodes
- the reaction gas flow path that overlaps with the portion twice and the length of the portion overlapping with the peripheral edge portion is equal to or less than a predetermined length
- the reaction gas flow path that overlaps the peripheral edge of the electrode and the length of the portion overlapping the peripheral edge is longer than the predetermined length is defined as the second reaction gas flow path
- the second reaction gas In the flow path the flow rate of the reactive gas flowing through the second reactive gas flow path is the first flow rate.
- An upstream flow path that includes a portion that contacts the peripheral edge
- a downstream flow path that includes a portion that first contacts the peripheral edge of the electrode when traced upstream from its downstream end
- a middle flow channel that is a portion other than the above, and the middle flow channel is configured not to overlap the peripheral edge of the electrode.
- the polymer electrolyte fuel cell As described above, in the polymer electrolyte fuel cell, a strong stress is applied to the portion of the polymer electrolyte membrane that faces the electrode peripheral portion (particularly, the catalyst layer peripheral portion) when viewed from the thickness direction of the separator. The relevant part of the polymer electrolyte membrane is crushed, the amount of cross leak of the reaction gas is increased, and radicals are generated from hydrogen peroxide which is a reaction byproduct. And it is thought that when the produced radical attacks the polymer electrolyte membrane, the polymer electrolyte membrane is damaged and deteriorated, and the performance of the fuel cell is lowered.
- the flow rate of the reaction gas flowing through the second reaction gas channel formed in the portion overlapping the electrode peripheral edge of the separator is reduced.
- the flow rate of the reaction gas supplied to the electrode periphery can be reduced by not forming the reaction gas flow path in the portion overlapping the electrode periphery of the separator.
- the amount of cross-leakage of the reaction gas, which is a raw material for hydrogen peroxide can be reduced, and the generation of radicals from hydrogen peroxide is reduced.
- the durability of the polymer electrolyte membrane can be improved, and the deterioration of the battery performance can be suppressed.
- the first reactive gas flow path has a fluid resistance of the reactive gas flowing through the first reactive gas flow path through the second reactive gas flow path. You may comprise so that it may become larger than the fluid resistance of the said reaction gas to flow.
- the plurality of reaction gas passages both the first reaction gas passage and the second reaction gas passage
- the reaction gas supply manifold hole Since it is connected to the manifold hole, the pressure loss of the first reaction gas channel and the second reaction gas channel is the same.
- the polymer electrolyte fuel cell according to the present invention is configured such that the fluid resistance of the reaction gas flowing through the first reaction gas channel is greater than that of the second reaction gas channel. Therefore, the flow rate of the reaction gas flowing through the first reaction gas channel is smaller than that of the second reaction gas channel. For this reason, in the polymer electrolyte fuel cell according to the present invention, the durability of the polymer electrolyte membrane can be improved, and the deterioration of the battery performance can be suppressed.
- the first reaction gas channel may be configured such that the cross-sectional area thereof is smaller than the cross-sectional area of the second reaction gas channel.
- the length of the first reactive gas flow channel is longer than that of the second reactive gas flow channel. You may be comprised so that it may become longer than length.
- the plurality of reaction gas flow paths may be formed so as to run in parallel with each other.
- the polymer electrolyte fuel cell according to the present invention may further include a reinforcing member, and the reinforcing member may be provided at a peripheral portion of the polymer electrolyte membrane as viewed from the thickness direction of the separator.
- a part of the reinforcing member is in contact with the other main surface of the catalyst layer, and when viewed from the thickness direction of the separator, the catalyst layer It may be arranged so as to overlap.
- the reinforcing member may be disposed so as not to overlap the catalyst layer when viewed from the thickness direction of the separator.
- the reinforcing member may be formed of a resin.
- the plurality of reaction gas flow paths may be formed on one main surface of the separator.
- the plurality of reaction gas flow paths may be formed on one main surface of the gas diffusion layer.
- the plurality of reaction gas flow paths may be formed on each of one main surface of the separator and one main surface of the gas diffusion layer.
- the polymer electrolyte fuel cell of the present invention deterioration of the polymer electrolyte membrane can be suppressed, durability can be improved, and deterioration of the fuel cell performance can be suppressed.
- FIG. 1 is a perspective view schematically showing a schematic configuration of a fuel cell stack including a polymer electrolyte fuel cell according to Embodiment 1 of the present invention.
- FIG. 2 is a cross-sectional view schematically showing a schematic configuration of the polymer electrolyte fuel cell in the fuel cell stack shown in FIG.
- FIG. 3 is a schematic diagram showing a schematic configuration of an anode separator of the polymer electrolyte fuel cell shown in FIG.
- FIG. 4 is a schematic diagram showing a schematic configuration of a cathode separator of the polymer electrolyte fuel cell shown in FIG.
- FIG. 5 is a cross-sectional view schematically showing a schematic configuration of the polymer electrolyte fuel cell according to Embodiment 2 of the present invention.
- FIG. 6 is a cross-sectional view schematically showing a schematic configuration of a polymer electrolyte fuel cell of Modification 1 in the polymer electrolyte fuel cell according to the second embodiment.
- FIG. 7 is a cross-sectional view schematically showing a schematic configuration of the polymer electrolyte fuel cell according to Embodiment 3 of the present invention.
- FIG. 8 is a schematic diagram showing a schematic configuration of the separator according to Embodiment 4 of the present invention.
- FIG. 9 is a cross-sectional view schematically showing a schematic configuration of the polymer electrolyte fuel cell according to Embodiment 4 of the present invention.
- FIG. 10 is a schematic diagram showing a schematic configuration of the separator according to Embodiment 5 of the present invention.
- FIG. 11 is a schematic diagram showing a schematic configuration of the separator according to Embodiment 6 of the present invention.
- FIG. 12 is a schematic diagram showing a schematic configuration of the separator according to Embodiment 7 of the present invention.
- FIG. 13 is a cross-sectional view schematically showing a schematic configuration of the fuel cell according to Embodiment 8 of the present invention.
- FIG. 14 is a schematic diagram showing a schematic configuration of electrodes in the fuel cell shown in FIG.
- FIG. 15 is a schematic diagram showing a schematic configuration of a separator in the fuel cell shown in FIG.
- FIG. 16 is a cross-sectional view schematically showing a schematic configuration of a fuel cell according to Modification 1 of Embodiment 8.
- FIG. 17 is a cross-sectional view schematically showing a schematic configuration of the fuel cell of Modification 2 of Embodiment 8.
- FIG. 18 is a cross-sectional view schematically showing a schematic configuration of the fuel cell according to Embodiment 9 of the present invention.
- FIG. 19 is a schematic diagram showing a schematic configuration of electrodes in a fuel cell according to Embodiment 9 of the present invention.
- FIG. 20 is a cross-sectional view schematically showing a schematic configuration of the fuel cell according to Embodiment 10 of the present invention.
- FIG. 21 is a schematic diagram showing a schematic configuration of a cell of a polymer electrolyte fuel cell disclosed in Patent Document 1. As shown in FIG.
- FIG. 1 is a perspective view schematically showing a schematic configuration of a fuel cell stack including a polymer electrolyte fuel cell (hereinafter simply referred to as a fuel cell) according to Embodiment 1 of the present invention.
- a fuel cell a polymer electrolyte fuel cell
- FIG. 1 the vertical direction of the fuel cell stack is shown as the vertical direction in the figure.
- a fuel cell stack 61 includes a cell stack 62 in which fuel cells 100 having a plate-like overall shape are stacked in the thickness direction, and a cell stack.
- Fastening (not shown) for fastening the first and second end plates 63 and 64 disposed at both ends of the 62 and the cell stack 62 and the first and second end plates 63 and 64 in the stacking direction of the fuel cell 100 And a tool.
- a current collecting plate and an insulating plate are disposed between the first end plate 63 and the cell stack 62 and between the second end plate 64 and the cell stack 62, respectively, but the illustration is omitted.
- the plate-like fuel cell 100 extends in parallel to the vertical plane, and the stacking direction of the fuel cells 100 is a horizontal direction.
- the fuel gas penetrates in the stacking direction of the fuel cell 100 of the cell stack 62 in the upper part of one side portion (the left side in the drawing: hereinafter referred to as the first side portion) of the cell stack 62.
- a supply manifold 131 is provided, and a cooling medium discharge manifold 136 is provided below the supply manifold 131.
- an oxidant is provided inside the upper portion of the cell stack 62 where the fuel gas supply manifold 131 is disposed on the first side so as to penetrate the cell stack 62 in the stacking direction of the fuel cells 100.
- a gas supply manifold 133 is provided, and similarly, an oxidant is provided inside the lower portion where the cooling medium discharge manifold 136 is disposed so as to penetrate in the stacking direction of the fuel cell 100 of the cell stack 62.
- a gas exhaust manifold 134 is provided. Further, cooling is performed so that the cell stack 62 penetrates in the stacking direction of the fuel cell 100 in the upper portion of the other side portion (the side portion on the right side of the drawing: hereinafter, the second side portion) of the cell stack 62.
- a medium supply manifold 135 is provided, and a fuel gas discharge manifold 132 is provided below the medium supply manifold 135 so as to penetrate the cell stack 62 in the stacking direction of the fuel cells 100.
- each manifold is provided with appropriate piping.
- the fuel gas, the oxidant gas, and the cooling medium are supplied to the fuel cell stack 61 through appropriate piping and discharged.
- FIG. 2 is a cross-sectional view schematically showing a schematic configuration of the fuel cell in the fuel cell stack shown in FIG.
- the fuel cell 100 according to Embodiment 1 includes an MEA (Membrane-Electrode-Assembly) 5, a gasket 7, an anode separator 6A, a cathode separator 6B, It has.
- MEA Membrane-Electrode-Assembly
- the MEA 5 includes a polymer electrolyte membrane 1 that selectively transports hydrogen ions, an anode electrode 4A, and a cathode electrode 4B.
- the polymer electrolyte membrane 1 has a substantially quadrangular (here, rectangular) shape, and an anode electrode 4A and a cathode are positioned on both sides of the polymer electrolyte membrane 1 so as to be located inward from the peripheral edge thereof. Electrodes 4B are provided respectively.
- manifold holes such as a fuel gas supply manifold hole 31 and a cooling medium supply manifold hole 35 are provided in the peripheral edge portion of the polymer electrolyte membrane 1 so as to penetrate in the thickness direction.
- the anode electrode 4A is provided on one main surface of the polymer electrolyte membrane 1, and is attached to a catalyst-supporting carbon made of carbon powder (conductive carbon particles) supporting a platinum-based metal catalyst (electrode catalyst) and to the catalyst-supporting carbon.
- the anode catalyst layer 2A containing the polymer electrolyte and the anode gas diffusion layer 3A having both gas permeability and conductivity are provided.
- the anode catalyst layer 2A is arranged such that one main surface is in contact with the polymer electrolyte membrane 1, and the anode gas diffusion layer 3A is arranged on the other main surface of the anode catalyst layer 2A.
- the cathode electrode 4B is provided on the other main surface of the polymer electrolyte membrane 1, and comprises a catalyst-carrying carbon and a catalyst-carrying carbon made of carbon powder (conductive carbon particles) carrying a platinum-based metal catalyst (electrode catalyst).
- a cathode catalyst layer 2B containing a polymer electrolyte attached to carbon and a cathode gas diffusion layer 3B provided on the cathode catalyst layer 2B and having both gas permeability and conductivity are provided.
- the cathode catalyst layer 2B is disposed such that one main surface is in contact with the polymer electrolyte membrane 1, and the cathode gas diffusion layer 3B is disposed on the other main surface of the cathode catalyst layer 2B.
- the anode catalyst layer 2A has an outer end located outside the outer end of the anode gas diffusion layer 3A (so that it protrudes).
- the cathode catalyst layer 2B is formed so that the outer end thereof is located outward from the outer end of the cathode gas diffusion layer 3B.
- the layer 2A may be formed such that the outer end thereof is positioned inward of the anode gas diffusion layer 3A, and the cathode catalyst layer 2B is positioned inward of the cathode gas diffusion layer 3B. It may be formed as follows.
- a gasket 7 is provided around the anode electrode 4A and the cathode electrode 4B (more precisely, the anode gas diffusion layer 3A and the cathode gas diffusion layer 3B) of the MEA 5.
- a pair of fluororubber made of doughnut-shaped with the polymer electrolyte membrane 1 interposed therebetween.
- manifold holes such as a fuel gas supply manifold hole 31 and a cooling medium supply manifold hole 35 including through holes in the thickness direction are provided.
- a conductive anode separator 6A and a cathode separator 6B are disposed so as to sandwich the MEA 5 and the gasket 7.
- MEA 5 is mechanically fixed, and when a plurality of fuel cells 100 are stacked in the thickness direction, MEA 5 is electrically connected.
- these separators 6A and 6B can use the metal excellent in heat conductivity and electroconductivity, graphite, or what mixed graphite and resin, for example, carbon powder and a binder (solvent).
- a mixture prepared by injection molding or a plate of titanium or stainless steel plated with gold can be used.
- a groove-like fuel gas flow path 8 is provided for allowing the fuel gas to flow therethrough.
- a groove-like cooling medium flow path 10 through which the cooling medium flows is provided on the surface (hereinafter referred to as an outer surface).
- a groove-like oxidant gas flow path 9 through which an oxidant gas flows is provided on one main surface (hereinafter referred to as an inner surface) of the cathode separator 6B that is in contact with the cathode electrode 4B.
- the other main surface (hereinafter referred to as an outer surface) is provided with a groove-like cooling medium flow path 10 through which the cooling medium flows.
- fuel gas and oxidant gas are supplied to the anode electrode 4A and the cathode electrode 4B, respectively, and these gases react to generate electricity and heat. Further, the generated heat is recovered by passing a cooling medium such as water or an antifreeze liquid (for example, an ethylene glycol-containing liquid) through the cooling medium flow path 10.
- a cooling medium such as water or an antifreeze liquid (for example, an ethylene glycol-containing liquid)
- the fuel cell 100 configured as described above may be used as a single cell (cell), or a plurality of fuel cells 100 may be stacked and used as the fuel cell stack 61. Further, when the fuel cells 100 are stacked, the cooling medium flow path 10 may be provided for every two to three cells. Further, when the cooling medium flow path 10 is not provided between the single cells, the separator sandwiched between the two MEAs 5 is provided, the fuel gas flow path 8 is provided on one main surface, and the oxidant gas flow is provided on the other main surface. A separator serving as an anode separator 6A and a cathode separator 6B provided with a passage 9 may be used.
- FIG. 3 is a schematic diagram showing a schematic configuration of the anode separator of the fuel cell shown in FIG.
- FIG. 4 is a schematic diagram showing a schematic configuration of the cathode separator of the fuel cell shown in FIG. 3 and 4, the vertical direction in the anode separator 6A and the cathode separator 6B is shown as the vertical direction in the drawings. Moreover, in FIG. 4, the peripheral part of the cathode electrode 4B is shown by hatching.
- the anode separator 6A has a plate shape and is formed in a substantially quadrangular shape (here, a rectangle), and each manifold hole such as the fuel gas supply manifold hole 31 is formed on the periphery thereof. It is provided so as to penetrate in the thickness direction.
- a fuel gas supply manifold hole (reactive gas supply manifold hole) 31 is provided in an upper portion of one side portion (hereinafter referred to as a first side portion) of the anode separator 6A, and a lower portion thereof. Is provided with a cooling medium discharge manifold hole 36.
- an oxidant gas supply manifold hole (reaction gas supply manifold hole) 33 is provided inside the upper portion where the fuel gas supply manifold hole 31 is disposed, and similarly, a cooling medium discharge manifold hole 36 is formed.
- An oxidant gas discharge manifold hole (reactive gas discharge manifold hole) 34 is provided on the inner side of the lower portion.
- a cooling medium supply manifold hole 35 is provided in the upper part of the other side part (hereinafter referred to as the second side part) of the anode separator 6A, and a fuel gas discharge manifold hole (reactive gas discharge) is provided in the lower part thereof.
- (Manifold hole) 32 is provided.
- a groove-like fuel gas flow path 8 is provided on the inner surface of the anode separator 6 ⁇ / b> A so as to connect the fuel gas supply manifold hole 31 and the fuel gas discharge manifold hole 32. Is formed.
- the fuel gas flow path 8 is composed of a plurality of (here, four) grooves, and the grooves are substantially composed of a straight portion 8a and a folded portion 8b. .
- the grooves constituting the fuel gas flow path 8 extend a distance in the horizontal direction from the fuel gas supply manifold hole 31 toward the second side portion, and extend a distance therebelow. Then, a distance in the horizontal direction extends from the reaching point toward the first side portion, and a distance in the lower direction extends therefrom. Then, the extension pattern is repeated once, and from there, it extends in the horizontal direction toward the second side so as to reach the fuel gas discharge manifold hole 32.
- Such a portion extending in the horizontal direction of the fuel gas flow path 8 constitutes a straight portion 8a, and a portion extending downward constitutes a folded portion 8b. As shown in FIGS.
- the portion between the groove (more precisely, the straight portion 8a) and the groove (more precisely, the straight portion 8a) constituting the fuel gas flow path 8 is the anode electrode 4A. 1st rib part 11 which contact
- the fuel gas flow path 8 is formed by a plurality of (here, four) grooves.
- the present invention is not limited to this, and one groove is formed on the inner surface of the anode separator 6A.
- the fuel gas flow path 8 may be used.
- the cathode separator 6 ⁇ / b> B is plate-shaped and is formed in a substantially quadrangular shape (here, a rectangle), and each manifold such as the fuel gas supply manifold hole 31 is provided at the peripheral portion thereof.
- the hole is provided so as to penetrate in the thickness direction. Since the arrangement of the manifold holes is the same as that of the anode separator 6A, detailed description thereof is omitted.
- a first connection channel 19, a second connection channel 20, and an oxidant gas channel 9 are formed on the inner surface of the cathode separator 6B.
- One end of the first connection channel 19 is connected to the oxidant gas supply manifold hole 33.
- One end of the second connection flow path 20 is connected to the oxidant gas discharge manifold hole 34.
- the first connection channel 19 and the second connection channel 20 are configured by a plurality of (here, 15) grooves and are formed to extend in the vertical direction.
- the other end of the first connection channel 19 is a portion that overlaps the outer periphery of the cathode electrode 4B (more precisely, the cathode gas diffusion layer 3B) when viewed from the thickness direction of the cathode separator 6B.
- the other end of the second connection channel 20 is a portion that overlaps with the outer periphery of the cathode electrode 4B (more precisely, the cathode gas diffusion layer 3B) when viewed from the thickness direction of the cathode separator 6B.
- the oxidant gas flow path 9 is composed of a plurality of (here, 15) grooves, and the plurality of grooves are linear so as to connect the first connection flow path 19 and the second connection flow path 20. Is formed.
- the plurality of oxidant gas flow paths 9 are formed so as to run in parallel with each other.
- running parallel to each other means that a plurality of oxidant gas flow paths are provided side by side. That is, it means that one oxidant gas flow path is specified from among a plurality of oxidant gas flow paths, and another oxidant gas flow path is provided along the specified oxidant gas flow path.
- the plurality of oxidant gas flow paths 9 are arranged such that the flow directions of the oxidant gases flowing through the respective flow paths coincide with each other from the upstream end toward the downstream end. It means that the gas flow path 9 is provided. Therefore, it is not necessary that the plurality of oxidant gas flow paths 9 are provided in complete alignment from the upstream end to the downstream end, and a portion in which the plurality of oxidant gas flow paths 9 are not provided in parallel with each other is provided. You may have.
- the oxidant gas flow paths 9 are formed so as to run in parallel with each other.
- the present invention is not limited to this, and the oxidant gas flow paths 9 may be formed so as not to run in parallel with each other. Good.
- the fuel gas flow path 8 and the oxidant gas flow path 9 are configured to be a so-called parallel flow.
- the parallel flow means that the fuel gas channel 8 and the oxidant gas channel 9 are macroscopically (as a whole) from upstream to downstream of the oxidant gas and the fuel gas as viewed from the thickness direction of the fuel cell 100. It is said that it is comprised so that the direction of the whole flow may mutually correspond.
- a portion between the grooves constituting the oxidant gas flow path 9 forms a second rib portion 12 that contacts the cathode electrode 4B.
- the oxidant gas flow path 9 includes a first oxidant gas flow path (first reaction gas flow path) 91 and a second oxidant gas flow path (second reaction gas flow path) 92. have.
- first oxidant gas flow path 91 overlaps the peripheral portion 40B of the cathode electrode 4B twice when viewed from the upstream end to the downstream end, and
- the length of the portion overlapping with the peripheral edge portion 40B is formed to be equal to or less than a predetermined length L.
- the first oxidant gas flow channel 91 first contacts the cathode electrode 4B when viewed from the thickness direction of the cathode separator 6B and when it follows the upstream end to the downstream.
- the portion 91A and the downstream end thereof are traced upstream, the portion 91B first comes into contact with the cathode electrode 4B, and the sum of the lengths of the portions 91A and 91B is equal to or less than a predetermined length L. Is formed.
- the peripheral edge portion 40B of the cathode electrode 4B refers to a region between the outer end of the cathode electrode 4B and a portion that is a predetermined distance N inward from the outer end.
- the peripheral portion 40B of the cathode electrode 4B refers to a region having a predetermined distance N from the outer end of the cathode electrode 4B.
- the predetermined distance N may be 5 mm or less, more preferably 3 mm or less, from the viewpoint of suppressing deterioration of the polymer electrolyte membrane 1.
- the peripheral portion 40B of the cathode electrode 4B may have an area that is 1/5 or less, more preferably 1/10 of the area of the cathode electrode 4B. It may be the following.
- the predetermined length L is preferably not less than 2 times and not more than 5 times the width (predetermined distance N) of the peripheral portion 40B of the cathode electrode 4B. That is, the predetermined length L is preferably 6 mm or more and 25 mm or less from the viewpoint of suppressing deterioration of the polymer electrolyte membrane 1.
- the outer end of the cathode electrode 4B is preferably based on the outer end of the cathode catalyst layer 2B because the electrochemical reaction of the reaction gas is performed in the cathode catalyst layer 2B.
- the second oxidizing gas channel 92 overlaps with the peripheral edge portion 40B of the cathode electrode 4B, and the length of the portion overlapping the peripheral edge portion 40B of the cathode electrode 4B is a predetermined length. It is formed to be longer than the length L.
- the second oxidant gas flow path 92 is configured such that the flow rate of the oxidant gas flowing through the second oxidant gas flow path 92 is greater than that of the oxidant gas flowing through the first oxidant gas flow path 91. It is configured to be less than the flow rate. Specifically, the fluid resistance of the oxidant gas flowing through the second oxidant gas flow path 92 is configured to be greater than the fluid resistance of the oxidant gas flowing through the first oxidant gas flow path 91.
- at least one oxidant gas flow path 9 out of the pair of oxidant gas flow paths 9 closest to the outer end of the cathode electrode 4B is more than the other oxidant gas flow paths 9. What is necessary is just to be comprised so that the flow volume of the oxidant gas to flow through may become small.
- the first oxidant gas flow channel 91 and the second oxidant gas flow channel 92 have their upstream ends connected to the oxidant gas supply manifold hole 33 via the first connection flow channel 19. ing.
- the first oxidant gas flow channel 91 and the second oxidant gas flow channel 92 are connected at their downstream ends to the oxidant gas discharge manifold hole 34 via the second connection flow channel 20.
- the pressure loss between the upstream end and the downstream end in the first oxidant gas flow channel 91 and the pressure loss between the upstream end and the downstream end in the second oxidant gas flow channel 92 are the same.
- the second oxidant gas channel 92 has a larger fluid resistance than the first oxidant gas channel 91, the flow rate of the oxidant gas flowing through the second oxidant gas channel 92 is small. .
- the second oxidant gas passage 92 is configured such that its cross-sectional area is smaller than the cross-sectional area of the first oxidant gas passage 91.
- the width of the second oxidant gas flow path 92 is configured to be smaller than the width of the first oxidant gas flow path 91.
- the cross-sectional area of the oxidant gas flow path 9 refers to a cross-sectional area in a direction perpendicular to the direction in which the oxidant gas flows.
- the width of the oxidant gas flow path 9 is a width in a direction perpendicular to the thickness direction of the cathode separator 6B and perpendicular to the direction in which the oxidant gas flows.
- the pair of outermost channels among the plurality of oxidant gas channels 9 each constitutes the second oxidant gas channel 92. It is not limited, and only one of the pair of outermost channels may be formed so that the flow rate is smaller than the other channels (that is, only one channel) May constitute the second oxidant gas flow path 92).
- one second oxidant gas flow path 92 is formed in the peripheral portion 40B on the first side portion side of the peripheral portion 40B of the cathode electrode 4B, and the second side.
- one second oxidant gas flow path 92 is formed in the peripheral edge part 40B on the part side, the present invention is not limited to this, and a plurality of second oxidant gas flow paths 92 are provided in the peripheral part 40B on the first side part side.
- a plurality of second oxidant gas flow paths 92 may be formed in the peripheral portion 40B on the second side portion side.
- the plurality of oxidant gas flows 9 are configured by only the first oxidant gas flow channel 91 and the second oxidant gas flow channel 92.
- a flow path that does not correspond to the second oxidant gas flow path 92 may be formed on the inner surface of the cathode separator 6B.
- the peripheral portion of the cathode electrode 4B (anode electrode 4A) of the polymer electrolyte membrane 1 when viewed from the thickness direction of the cathode separator 6B, the peripheral portion of the cathode electrode 4B (anode electrode 4A) of the polymer electrolyte membrane 1 (particularly, the cathode catalyst layer 2B (anode catalyst layer 2A)).
- the peripheral portion of the fuel cell 100 is likely to be damaged or deteriorated, which is considered to reduce the performance of the fuel cell 100.
- the second oxidant gas flow path formed in the portion overlapping the peripheral edge portion 40B of the cathode electrode 4B in the cathode separator 6B.
- the amount of cross leak of the reaction gas (in particular, the oxidant gas here) can be reduced in the portion overlapping the peripheral edge portion 40B of the polymer electrolyte membrane 1, Generation of radicals from hydrogen peroxide is reduced.
- the durability of the polymer electrolyte membrane 1 can be improved, and the deterioration of the battery performance can be suppressed.
- the fuel gas flow path 8 is formed in a serpentine shape, but is not limited thereto, and may be formed in a straight line like the oxidant gas flow path 9. Further, although the oxidant gas flow path 9 is formed in a straight line shape, the present invention is not limited to this, and it may be formed in a serpentine shape like the fuel gas flow path 8.
- FIG. 5 is a cross-sectional view schematically showing a schematic configuration of the fuel cell according to Embodiment 2 of the present invention.
- the fuel cell 100 according to Embodiment 2 of the present invention has the same basic configuration as the fuel cell 100 according to Embodiment 1, but is further provided with a reinforcing member 13. Specifically, the reinforcing member 13 is disposed between the polymer electrolyte membrane 1 and the gasket 7 so as to be sandwiched between these members.
- the reinforcing member 13 is formed in a substantially rectangular and donut shape when viewed from the thickness direction of the cathode separator 6B. Further, the reinforcing member 13 is disposed so that the inner peripheral end thereof is located inside the outer end of the anode catalyst layer 2A or the cathode catalyst layer 2B when viewed from the thickness direction of the cathode separator 6B. In other words, the reinforcing member 13 is disposed so that the inner peripheral portion of the reinforcing member 13 and the outer peripheral portion of the anode catalyst layer 2A or the cathode catalyst layer 2B overlap each other when viewed from the thickness direction of the cathode separator 6B. .
- the reinforcing member 13 is disposed so that a part thereof is in contact with the other main surface of the anode catalyst layer 2A or the cathode catalyst layer 2B. In other words, the reinforcing member 13 is arranged so that a part thereof rides on the other main surface of the anode catalyst layer 2A or the cathode catalyst layer 2B.
- the reinforcement of the polymer electrolyte membrane 1 is performed as described above. A portion facing (overlapping) the inner periphery of the member 13 may be deteriorated.
- the peripheral edge portion 40B of the cathode electrode 4B is defined so as to include the inner periphery of the reinforcing member 13 when viewed from the thickness direction of the cathode separator 6B.
- the peripheral edge portion 40B of the cathode electrode 4B has an inner peripheral end of the reinforcing member 13 and a portion separated from the inner peripheral end of the reinforcing member 13 by a predetermined distance N when viewed from the thickness direction of the cathode separator 6B. Is preferably defined as the region between.
- the predetermined distance N may be 5 mm or less, more preferably 3 mm or less, from the viewpoint of suppressing deterioration of the polymer electrolyte membrane 1.
- the reinforcing member 13 and the anode catalyst layer 2 ⁇ / b> A or the cathode catalyst layer 2 ⁇ / b> B partially overlap each other when viewed from the thickness direction of the cathode separator 6 ⁇ / b> B.
- the peripheral edge portion 40B of the cathode electrode 4B is between the inner peripheral end of the reinforcing member 13 and a portion away from the inner peripheral end of the reinforcing member 13 by a predetermined distance N.
- the peripheral portion 40B of the cathode electrode 4B is It is defined as a region between the outer end of the cathode electrode 4B and a portion separated by a predetermined distance N inward from the outer end.
- FIG. 6 is a cross-sectional view schematically showing a schematic configuration of a fuel cell according to Modification 1 of Embodiment 2.
- the outer end of the anode catalyst layer 2A is positioned inward of the outer end of the anode gas diffusion layer 3A when viewed from the thickness direction of the cathode separator 6B.
- the outer end of the cathode catalyst layer 2B is formed so as to be located inward of the outer end of the cathode gas diffusion layer 3B.
- the reinforcing member 13 is disposed so as not to overlap the anode catalyst layer 2A or the cathode catalyst layer 2B when viewed from the thickness direction of the cathode separator 6B.
- FIG. 7 is a cross-sectional view schematically showing a schematic configuration of the fuel cell according to Embodiment 3 of the present invention.
- the basic configuration of the fuel cell 100 according to Embodiment 3 of the present invention is the same as that of the fuel cell 100 according to Embodiment 1, but the second oxidation of the oxidant gas flow path 9 is performed.
- the configuration of the agent gas flow path 92 is different.
- the second oxidant gas channel 92 is formed so that the depth thereof is shallower than the depth of the first oxidant gas channel 91.
- the cross-sectional area of the second oxidant gas channel 92 can be made smaller than that of the first oxidant gas channel 91. That is, the flow rate of the oxidant gas flowing through the second oxidant gas flow channel 92 can be made smaller than that of the first oxidant gas flow channel 91.
- FIG. 8 is a schematic diagram showing a schematic configuration of a separator in a fuel cell according to Embodiment 4 of the present invention
- FIG. 9 schematically shows a schematic configuration of a fuel cell according to Embodiment 4 of the present invention. It is sectional drawing.
- the up-down direction in a separator is represented as the up-down direction in a figure, and the peripheral part of the electrode is shown by hatching.
- the fuel cell 100 according to the fourth embodiment of the present invention has the same basic configuration as the fuel cell 100 according to the first embodiment, but the The difference is that the second oxidant gas flow path 92 is not provided. That is, in the separator according to the fourth embodiment, when viewed from the thickness direction of the separator, when the plurality of oxidant gas flow paths 9 are traced from the upstream end to the downstream, first, the peripheral edge portion 40B of the cathode electrode 4B.
- An upstream flow path 90a including a portion 91A in contact with the upstream flow path 90a, a downstream flow path 90b including a portion 91B in contact with the peripheral edge portion 40B of the cathode electrode 4B first when the upstream end is traced upstream, and an upstream flow path 90a And a midstream channel 90c that is a part other than the downstream channel 90b, and the midstream channel 90c is configured not to overlap the peripheral edge portion 40B of the cathode electrode 4B.
- the upstream flow path 90a has one end as an upstream end of the oxidant gas flow path 9 and a portion overlapping the cathode electrode 4B when viewed from the thickness direction of the cathode separator 6B, and the other end is expressed by the formula L1 ⁇ ⁇ ( 1/3) ⁇ L2 ⁇ and a portion between them.
- L1 indicates the flow path length of the upstream flow path 90a of the oxidant gas flow path 9
- L2 indicates the total flow path length of the oxidant gas flow path 9.
- the downstream flow path 90b has one end as a portion that overlaps the cathode electrode 4B when viewed from the thickness direction of the cathode separator 6B, which is the downstream end of the oxidant gas flow path 9, and the other end is represented by the formula: L3 ⁇ ⁇ (1 / 3) A portion satisfying ⁇ L2 ⁇ and a portion between them.
- L3 indicates the channel length of the downstream channel 90b of the oxidant gas channel 9.
- the second oxidant gas flow is applied to the first side portion and the second side portion of the peripheral edge portion 40B of the cathode electrode 4B. Since the path 92 is not provided, the oxidant gas is not supplied to the portion of the peripheral edge portion 40B. For this reason, when viewed from the thickness direction of the cathode separator 6B, the amount of cross leakage is reduced at the portion facing the first side portion and the second side portion of the peripheral edge portion 40B in the polymer electrolyte membrane 1. Less and the production of radicals from hydrogen peroxide is further reduced. Therefore, in the fuel cell 100 according to Embodiment 4, the durability of the polymer electrolyte membrane 1 can be improved, and the deterioration of the battery performance can be suppressed.
- FIG. 10 is a schematic diagram showing a schematic configuration of the separator in the fuel cell according to Embodiment 5 of the present invention.
- the up-down direction in a separator is represented as the up-down direction in a figure, and the peripheral part of the electrode is shown by hatching.
- the separator (here, cathode separator 6B) in fuel cell 100 according to Embodiment 5 of the present invention is the separator (here, cathode separator 6B) in fuel cell 100 according to Embodiment 1.
- the basic configuration is the same, but the configuration of the second oxidizing gas channel 92 is different.
- the second oxidant gas channel 92 is configured to have the same cross-sectional area as the first oxidant gas channel 91, but the length of the channel is the first oxidant gas channel 91. It is configured to be longer than the agent gas passage 91.
- the second oxidant gas flow path 92 is formed in a serpentine shape as viewed from the thickness direction of the cathode separator 6B.
- the flow rate of the oxidant gas flowing through the second oxidant gas flow channel 92 can be made smaller than the flow rate of the oxidant gas flowing through the first oxidant gas flow channel 91. For this reason, even the fuel cell 100 according to the fifth embodiment has the same effects as the fuel cell 100 according to the first embodiment.
- FIG. 11 is a schematic diagram showing a schematic configuration of a separator in a fuel cell according to Embodiment 6 of the present invention.
- the up-down direction in a separator is represented as the up-down direction in a figure, and the peripheral part of the electrode is shown by hatching.
- the separator (here, cathode separator 6B) in fuel cell 100 according to Embodiment 6 of the present invention is the separator (here, cathode separator 6B) in fuel cell 100 according to Embodiment 1.
- the basic configuration is the same except that a plurality of oxidant gas flow paths 9 are formed in a serpentine shape.
- the plurality of oxidant gas flow paths 9 are formed in the same manner as the fuel gas flow path 8 of the fuel cell 100 according to Embodiment 1, and are substantially composed of the straight line portion 9a and the folded portion 9b. It is configured.
- the plurality of oxidant gas flow paths 9 includes a first oxidant gas flow path 91 and a second oxidant gas flow path 92, and the second oxidant gas flow path 92 has a cross-sectional area of
- the first oxidizing gas channel 91 is configured so as to be smaller than the cross-sectional area (here, the width of the channel is reduced).
- the cross-sectional area is made smaller than that of the first oxidant gas channel 91 in all parts of the second oxidant gas channel 92.
- the cross-sectional area of the second oxidant gas flow path 92 that overlaps the peripheral edge 40B of the cathode electrode 4B is smaller than that of the first oxidant gas flow path 91 when viewed from the thickness direction of the cathode separator 6B.
- the cross-sectional area of other portions may be configured to be the same as that of the first oxidant gas flow path 91.
- the second oxidant gas flow path 92 is configured such that the width of the flow path is smaller than the width of the flow path of the first oxidant gas flow path 91.
- the depth of the channel may be configured to be shallower than the depth of the first oxidant gas channel 91.
- both the first oxidant gas flow channel 91 and the second oxidant gas flow channel 92 are formed in a serpentine shape, but the oxidant flowing through the second oxidant gas flow channel 92 is used. If the flow rate of the gas can be made smaller than the flow rate of the oxidant gas flowing through the first oxidant gas flow channel 91, the shape of the flow channel is not limited.
- the first oxidant gas flow channel 91 may be formed in a straight shape
- the second oxidant gas flow channel 92 may be formed in a serpentine shape.
- the portion 9a and / or the folded portion 9b is further meandered like the second oxidant gas flow path 92 of the fifth embodiment, and the length of the flow path is the flow path of the first oxidant gas flow path 91. You may form so that it may become longer than this length.
- FIG. 12 is a schematic diagram showing a schematic configuration of the separator in the fuel cell according to Embodiment 7 of the present invention.
- the vertical direction of the separator is shown as the vertical direction in the figure, and the peripheral edge of the electrode is hatched.
- the separator (here, cathode separator 6B) in the fuel cell according to Embodiment 7 of the present invention is basically the same as the separator (here, cathode separator 6B) in the fuel cell according to Embodiment 1.
- a manifold (hole) for supplying oxidant gas to the first oxidant gas channel 91 and a manifold (hole) for supplying oxidant gas to the second oxidant gas channel 92 are provided. Is different.
- a first oxidant gas supply manifold hole 33A is provided in the upper part of the cathode separator 6B.
- the first oxidant gas supply manifold hole 33A and the fuel gas supply manifold hole 31 and the first oxidant gas supply manifold hole 33A are provided.
- a second oxidizing gas supply manifold hole 33B is provided between the agent gas supply manifold hole 33A and the cooling medium supply manifold hole 35, respectively.
- the upstream end of the first oxidant gas passage 91 is connected to the first oxidant gas supply manifold hole 33A, and the downstream end thereof is connected to the oxidant gas discharge manifold hole 34.
- the upstream end of the second oxidant gas flow path 92 is connected to the second oxidant gas supply manifold hole 33 ⁇ / b> B, and the downstream end thereof is connected to the oxidant gas discharge manifold hole 34.
- the pressure of the oxidant gas supplied to the second oxidant gas flow path 92 is preferably equal to or lower than the pressure of the oxidant gas supplied to the first oxidant gas flow path 91.
- the pressure in the second oxidant gas supply manifold hole 33B (second oxidant gas supply manifold hole 33B formed by connecting the second oxidant gas supply manifold hole 33B) is set to the first oxidant gas supply manifold hole 33A ( It is preferable that the pressure be equal to or lower than the pressure in the first oxidant gas supply manifold) formed by connecting the first oxidant gas supply manifold holes 33A.
- the flow rate of the oxidant gas supplied to the second oxidant gas supply manifold hole 33B (flowing through the second oxidant gas supply manifold hole 33B) is supplied to the first oxidant gas supply manifold hole 33A.
- the flow rate of the oxidant gas (which flows through the first oxidant gas supply manifold hole 33A) is preferably equal to or lower than the flow rate.
- the second oxidant gas channel 92 is configured such that the width of the channel is smaller than the width of the channel of the first oxidant gas channel 91.
- the depth of the channel may be configured to be shallower than the depth of the first oxidant gas channel 91.
- the oxidant gas flow path 9 is formed in a straight line, but the present invention is not limited to this.
- the first oxidant gas flow path 91 may be formed in a straight line
- the second oxidant gas flow path 92 may be formed in a serpentine shape.
- the oxidizing gas channel 9 (both the first oxidizing gas channel 91 and the second oxidizing gas channel 92) may be formed in a serpentine shape.
- FIG. 13 is a cross-sectional view schematically showing a schematic configuration of the fuel cell according to Embodiment 8 of the present invention.
- FIG. 14 is a schematic diagram showing a schematic configuration of electrodes in the fuel cell shown in FIG.
- FIG. 15 is a schematic diagram showing a schematic configuration of a separator in the fuel cell shown in FIG.
- the up-down direction in a separator is represented as the up-down direction in a figure, and the peripheral part of the electrode is shown by hatching.
- the vertical direction of the electrode is represented as the vertical direction in the figure.
- the fuel cell 100 according to Embodiment 8 of the present invention has the same basic configuration as the fuel cell 100 according to Embodiment 1, but the oxidant gas flow path 9 is The difference is that the cathode gas diffusion layer 3B of the cathode electrode 4B is provided. Further, in the fuel cell 100 according to Embodiment 8, the shapes of the first connection channel 19 and the second connection channel 20 are different from those of the fuel cell 100 according to Embodiment 1.
- the oxidant gas flow path 9 is provided on the main surface (hereinafter referred to as the outer surface) that contacts the cathode separator 6B of the cathode gas diffusion layer 3B.
- the oxidant gas channel 9 is formed in a straight line so as to extend from the upper end to the lower end of the cathode gas diffusion layer 3B.
- a portion between the oxidant gas flow path 9 and the oxidant gas flow path 9 on the outer surface of the cathode gas diffusion layer 3 ⁇ / b> B constitutes the second rib portion 12.
- the cathode gas diffusion layer 3B is composed of a sheet containing a binder resin and conductive particles without using a carbon fiber base material impregnated with a resin used in a gas diffusion layer in a conventional fuel cell.
- the binder resin include a fluororesin
- the conductive particles include particles made of carbon.
- Fluororesin includes PTFE (polytetrafluoroethylene), FEP (tetrafluoroethylene / hexafluoropropylene copolymer), PVDF (polyvinylidene fluoride), ETFE (tetrafluoroethylene / ethylene copolymer), PCTFE (polyethylene). Chlorotrifluoroethylene), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer) and the like, and PTFE is preferred from the viewpoints of heat resistance, water repellency and chemical resistance.
- the raw material of PTFE includes a dispersion and a powdery shape, but the dispersion is preferable from the viewpoint of workability.
- examples of the carbon material include graphite, carbon black, activated carbon and the like, and these materials may be used alone or in combination with a plurality of materials.
- the raw material form of the carbon material may be any shape such as powder, fiber, and granule.
- the cathode gas diffusion layer 3B preferably contains 5% by weight or more of a binder resin from the viewpoint of exerting a function as a binder, so that the cathode gas diffusion layer 3B has a uniform thickness. From the viewpoint of simplifying the conditions during the rolling process, it is preferably contained at 50% by weight or less. Further, from the same viewpoint as described above, it is more preferably contained in an amount of 10 to 30% by weight.
- the cathode gas diffusion layer 3B may contain a dispersion solvent, a surfactant, and the like in addition to the binder resin and the conductive particles.
- a dispersion solvent include water, alcohols such as methanol and ethanol, and glycols such as ethylene glycol.
- the surfactant include nonionic compounds such as polyoxyethylene alkyl ether and amphoteric ions such as alkylamine oxide.
- the amount of the dispersion solvent and the amount of the surfactant are determined based on the conductive particle material (carbon material) constituting the cathode gas diffusion layer 3B, the kind of the binder resin (fluororesin), the binder resin (fluororesin) and the conductive particles ( It can be selected as appropriate depending on the compounding ratio of carbon).
- the binder resin (fluororesin) and the conductive particles (carbon) tend to be uniformly dispersed, but the fluidity tends to increase and it becomes difficult to form a sheet. is there.
- the cathode gas diffusion layer 3B is manufactured by kneading, extruding, rolling, and firing a mixture containing a binder resin and conductive particles. Specifically, carbon, which is conductive particles, a dispersion solvent, and a surfactant are introduced into a stirrer / kneader, and then kneaded, pulverized, and granulated to disperse the carbon in the dispersed solvent. Next, the fluororesin as the binder resin is further dropped into a stirrer / kneader and stirred and kneaded to disperse the carbon and the fluororesin.
- the obtained kneaded material is rolled to form a sheet, and fired to remove the dispersion solvent and the surfactant, thereby producing a sheet for forming the cathode gas diffusion layer 3B.
- channel used as the oxidant gas flow path 9 is formed in the main surface of the sheet
- the cathode gas diffusion layer 3B is obtained.
- the surfactant can be appropriately selected depending on the material of the conductive particles (carbon material) and the type of the dispersion solvent, and the surfactant need not be used.
- the cathode gas diffusion layer 3B thus manufactured has a lower porosity than the carbon fiber base material impregnated with the resin used in the gas diffusion layer in the conventional fuel cell, but the reaction gas (oxidation gas) The agent gas) is configured to have a porosity enough to move. For this reason, even the cathode gas diffusion layer 3B manufactured by the above manufacturing method sufficiently fulfills the role as a gas diffusion layer.
- the first connection channel 19 extends in the vertical direction so that the other end is located below the upper end of the cathode gas diffusion layer 3B when viewed from the thickness direction of the cathode separator 6B. It is formed as follows.
- the second connection flow path 20 is formed to extend in the vertical direction so that the other end is located above the lower end of the cathode gas diffusion layer 3B when viewed from the thickness direction of the cathode separator 6B. .
- the upstream end of the oxidant gas flow path 9 communicates with the first connection flow path 19, and the downstream end of the oxidant gas flow path 9 is the second end. It communicates with the connection channel 20. Therefore, the oxidant gas is supplied from the oxidant gas supply manifold hole 33 to the oxidant gas flow path 9 through the first connection flow path 19. Then, the oxidant gas flowing through the oxidant gas flow path 9 is discharged to the oxidant gas discharge manifold hole 34 via the second connection flow path 20.
- FIG. 16 is a cross-sectional view schematically showing a schematic configuration of a fuel cell according to Modification 1 of Embodiment 8.
- the basic configuration of the fuel cell 100 of Modification 1 is the same as that of the fuel cell 100 according to Embodiment 8, but the second oxidant gas flow path 92 is provided in the cathode separator 6B. Is different.
- FIG. 17 is a cross-sectional view schematically showing a schematic configuration of the fuel cell of Modification 2 of Embodiment 8.
- FIG. 17 is a cross-sectional view schematically showing a schematic configuration of the fuel cell of Modification 2 of Embodiment 8.
- the basic configuration of the fuel cell 100 of Modification 2 is the same as that of the fuel cell 100 according to Embodiment 8, but the first oxidant gas flow path 91 is provided in the cathode separator 6B. Is different.
- FIG. 18 is a cross-sectional view schematically showing a schematic configuration of the fuel cell according to Embodiment 9 of the present invention.
- FIG. 19 is a schematic diagram showing a schematic configuration of electrodes in a fuel cell according to Embodiment 9 of the present invention.
- the vertical direction of the electrode is represented as the vertical direction in the drawing, and the peripheral portion of the electrode is indicated by hatching.
- the fuel cell 100 according to Embodiment 9 of the present invention has the same basic configuration as the fuel cell 100 according to Embodiment 8, but the oxidant gas flow path 9 The difference is that the second oxidant gas flow path 92 is not provided. That is, in the separator according to the ninth embodiment, when viewed from the thickness direction of the separator, the plurality of oxidant gas flow paths 9 are first the peripheral edge 40B of the cathode electrode 4B when the downstream from the upstream end thereof is followed.
- An upstream flow path 90a including a portion 91A that contacts the upstream flow path 90a, and a downstream flow path 90b that includes a portion 91B that first contacts the peripheral edge 40B of the cathode electrode 4B when the downstream end thereof is traced upstream.
- a midstream channel 90c that is a part other than the downstream channel 90b, and the midstream channel 90c is configured not to overlap the peripheral edge portion 40B of the cathode electrode 4B.
- the second oxidant gas flow is provided in the first side portion side portion and the second side portion side portion of the peripheral edge portion 40B in the cathode electrode 4B. Since the path 92 is not provided, the oxidant gas is not supplied to the portion of the peripheral edge portion 40B. For this reason, when viewed from the thickness direction of the cathode separator 6B, the amount of cross leakage is reduced at the portion facing the first side portion and the second side portion of the peripheral edge portion 40B in the polymer electrolyte membrane 1. Less and the production of radicals from hydrogen peroxide is further reduced. Therefore, in the fuel cell 100 according to Embodiment 9, the durability of the polymer electrolyte membrane 1 can be improved, and the deterioration of the battery performance can be suppressed.
- FIG. 20 is a cross-sectional view schematically showing a schematic configuration of the fuel cell according to Embodiment 10 of the present invention.
- the basic configuration of the fuel cell 100 according to Embodiment 10 of the present invention is the same as that of the fuel cell 100 according to Embodiment 1, but the oxidant gas flow path 9 is a cathode gas.
- the difference is that it is provided in both the diffusion layer 3B and the cathode separator 6B.
- the oxidant gas flow path 9 (hereinafter referred to as GDL side oxidant gas flow path 9) provided in the cathode gas diffusion layer 3B and the oxidant gas flow path 9 (hereinafter referred to as separator) provided in the cathode separator 6B.
- Side oxidant gas flow paths 9) are formed so as to overlap each other when viewed from the thickness direction of the cathode separator 6B.
- the fuel cell 100 according to the tenth embodiment configured as described above has the same effects as the fuel cell 100 according to the first embodiment.
- the GDL-side oxidant gas flow path 9 and the separator-side oxidant gas flow path 9 are formed so as to overlap each other when viewed from the thickness direction of the cathode separator 6B.
- the present invention is not limited to this. . If the oxidant gas flows through each of the GDL side oxidant gas flow path 9 and the separator side oxidant gas flow path 9, the GDL side oxidant gas flow path 9 and the separator side oxidant gas flow path
- the channel 9 may be formed so as to have portions that do not overlap each other when viewed from the thickness direction of the cathode separator 6B.
- the second oxidant gas flow path 92 is provided in both the cathode gas diffusion layer 3B and the cathode separator 6B.
- the present invention is not limited to this.
- the second oxidant gas flow path 92 may be provided only in the cathode gas diffusion layer 3B.
- the second oxidant gas flow path 92 may be provided only in the cathode separator 6B.
- Embodiments 1 to 10 only the cathode separator 6B is used as the separator according to the present invention.
- the present invention is not limited to this, and only the anode separator 6A is the separator according to the present invention.
- both the anode separator 6A and the cathode separator 6B may be used as the separator according to the present invention.
- a partial cross-sectional area of the second reaction gas channel is the first reaction gas channel (first oxidant gas flow). It may be formed so as to be larger than the cross-sectional area of the passage 91).
- the polymer electrolyte fuel cell of the present invention can suppress deterioration of the polymer electrolyte membrane and improve durability, and can suppress deterioration in performance of the fuel cell. Useful in the field of batteries.
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Abstract
Description
[燃料電池スタックの構成]
図1は、本発明の実施の形態1に係る高分子電解質形燃料電池(以下、単に燃料電池という)を備える、燃料電池スタックの概略構成を模式的に示す斜視図である。なお、図1において、燃料電池スタックの上下方向を図における上下方向として表している。
次に、本発明の実施の形態1に係る高分子電解質形燃料電池の構成について、図2を参照しながら説明する。
次に、アノードセパレータ6A及びカソードセパレータ6Bについて、図2乃至図4を参照しながら詳細に説明する。
次に、本実施の形態1に係る燃料電池100の作用効果について、図1乃至図4を参照しながら説明する。
図5は、本発明の実施の形態2に係る燃料電池の概略構成を模式的に示す断面図である。
次に、本実施の形態2に係る燃料電池100の変形例について説明する。
図7は、本発明の実施の形態3に係る燃料電池の概略構成を模式的に示す断面図である。
図8は、本発明の実施の形態4に係る燃料電池におけるセパレータの概略構成を示す模式図であり、図9は、本発明の実施の形態4に係る燃料電池の概略構成を模式的に示す断面図である。なお、図8においては、セパレータにおける上下方向を図における上下方向として表し、電極の周縁部をハッチングで示している。
図10は、本発明の実施の形態5に係る燃料電池におけるセパレータの概略構成を示す模式図である。なお、図10においては、セパレータにおける上下方向を図における上下方向として表し、電極の周縁部をハッチングで示している。
図11は、本発明の実施の形態6に係る燃料電池におけるセパレータの概略構成を示す模式図である。なお、図11においては、セパレータにおける上下方向を図における上下方向として表し、電極の周縁部をハッチングで示している。
図12は、本発明の実施の形態7に係る燃料電池におけるセパレータの概略構成を示す模式図である。なお、図12においては、セパレータにおける上下方向を図における上下方向として表し、電極の周縁部をハッチングで示している。
図13は、本発明の実施の形態8に係る燃料電池の概略構成を模式的に示す断面図である。図14は、図13に示す燃料電池における電極の概略構成を示す模式図である。図15は、図13に示す燃料電池におけるセパレータの概略構成を示す模式図である。
次に、本実施の形態8に係る燃料電池100の変形例について説明する。
図17は、本実施の形態8における変形例2の燃料電池の概略構成を模式的に示す断面図である。
図18は、本発明の実施の形態9に係る燃料電池の概略構成を模式的に示す断面図である。図19は、本発明の実施の形態9に係る燃料電池における電極の概略構成を示す模式図である。なお、図19においては、電極における上下方向を図における上下方向として表し、電極の周縁部をハッチングで示している。
図20は、本発明の実施の形態10に係る燃料電池の概略構成を模式的に示す断面図である。
2A アノード触媒層
2B カソード触媒層
3A アノードガス拡散層
3B カソードガス拡散層
4A アノード電極
4B カソード電極
5 MEA(Membrane-Electrode-Assembly:膜-電極接合体)
6A アノードセパレータ
6B カソードセパレータ
7 ガスケット
8 燃料ガス流路
8a 直線部
8b 折り返し部
9 酸化剤ガス流路
9a 直線部
9b 折り返し部
10 冷却媒体流路
11 第1リブ部
12 第2リブ部
13 補強部材
19 第1接続流路
20 第2接続流路
31 燃料ガス供給マニホールド孔
32 燃料ガス排出マニホールド孔
33 酸化剤ガス供給マニホールド孔
33A 第1酸化剤ガス供給マニホールド孔
33B 第2酸化剤ガス供給マニホールド孔
34 酸化剤ガス排出マニホールド孔
35 冷却媒体供給マニホールド孔
36 冷却媒体排出マニホールド孔
40B 周縁部
61 燃料電池スタック
62 セル積層体
63 第1の端板
64 第2の端板
91 第1酸化剤ガス流路
91 部分91A
91 部分91B
92 第2酸化剤ガス流路
100 燃料電池
131 燃料ガス供給マニホールド
132 燃料ガス排出マニホールド
133 酸化剤ガス供給マニホールド
134 酸化剤ガス排出マニホールド
135 冷却媒体供給マニホールド
136 冷却媒体排出マニホールド
200 セル
201 高分子膜
201P 部分
201W 酸素極境界膜部分、燃料極境界膜部分
202C 酸素極触媒層
203C 燃料極触媒層
204 補強部材
204E 内側端部
205 補強部材
205E 内側端部
Claims (12)
- 高分子電解質膜と該高分子電解質膜を挟む一対の電極を有する膜-電極接合体と、
板状に形成され、導電性を有するセパレータと、を備え、
前記電極は、一方の主面が前記高分子電解質膜と接触する触媒層とガス拡散層を有し、前記セパレータの厚み方向から見て、その外周が前記高分子電解質膜の外周より内方に位置するように形成され、
前記膜-電極接合体は、一対の前記セパレータに挟まれ、
前記セパレータは、その主面に厚み方向に貫通するように反応ガス供給マニホールド孔と反応ガス排出マニホールド孔が形成され、前記電極と接触する一方の主面には、前記反応ガス供給マニホールド孔に接続された溝状の第1接続流路と、前記反応ガス排出マニホールド孔に接続された溝状の第2接続流路と、が複数形成され、
前記セパレータ及び前記ガス拡散層の少なくとも一方の主面には、一端が前記第1接続流路と連通し、他端が前記第2接続流路と連通する溝状の反応ガス流路が複数形成され、
前記複数の反応ガス流路は、
前記セパレータの厚み方向から見て、その上流端から下流端に辿った場合に、前記電極の周縁部と2回重なり、かつ、当該周縁部と重なる部分の長さが所定の長さ以下である反応ガス流路を第1反応ガス流路と定義し、
その上流端から下流端に辿った場合に、前記電極の周縁部と重なり、かつ、当該周縁部と重なる部分の長さが前記所定の長さより長い反応ガス流路を第2反応ガス流路と定義した場合に、
前記第2反応ガス流路は、該第2反応ガス流路を通流する反応ガスの流量の方が前記第1反応ガス流路を通流する前記反応ガスの流量よりも小さくなるように構成されている、
又は、前記セパレータの厚み方向から見て、その上流端から下流に辿った場合に最初に前記電極の周縁部と接触する部分を含む上流流路と、その下流端から上流に辿った場合に最初に前記電極の周縁部と接触する部分を含む下流流路と、前記上流流路及び前記下流流路以外の部分である中流流路と、を有し、前記中流流路が、前記電極の周縁部と重ならないように構成されている、高分子電解質形燃料電池。 - 前記第2反応ガス流路は、該第2反応ガス流路を通流する前記反応ガスの流体抵抗が前記第1反応ガス流路を通流する前記反応ガスの流体抵抗よりも大きくなるように構成されている、請求項1に記載の高分子電解質形燃料電池。
- 前記第2反応ガス流路は、その断面積が前記第1反応ガス流路の断面積よりも小さくなるように構成されている、請求項1又は2に記載の高分子電解質形燃料電池。
- 前記第2反応ガス流路は、該第2反応ガス流路の流路の長さの方が前記第1反応ガス流路の流路の長さよりも長くなるように構成されている、請求項1~3のいずれか1項に記載の高分子電解質形燃料電池。
- 前記複数の反応ガス流路は、互いに並走するように形成されている、請求項1~4のいずれか1項に記載の高分子電解質形燃料電池。
- 補強部材をさらに備え、
前記補強部材は、前記セパレータの厚み方向から見て、前記高分子電解質膜の周縁部に設けられている、請求項1~5のいずれか1項に記載の高分子電解質形燃料電池。 - 前記補強部材は、その一部が、前記触媒層の他方の主面と接触し、かつ、前記セパレータの厚み方向から見て、前記触媒層と重なるように配設されている、請求項6に記載の高分子電解質形燃料電池。
- 前記補強部材は、前記セパレータの厚み方向から見て、前記触媒層と重ならないように配設されている、請求項6に記載の高分子電解質形燃料電池。
- 前記補強部材は、樹脂で形成されている、請求項6に記載の高分子電解質形燃料電池。
- 前記複数の反応ガス流路は、前記セパレータの一方の主面に形成されている、請求項1~9のいずれか1項に記載の高分子電解質形燃料電池。
- 前記複数の反応ガス流路は、前記ガス拡散層の一方の主面に形成されている、請求項1~9のいずれか1項に記載の高分子電解質形燃料電池。
- 前記複数の反応ガス流路は、前記セパレータの一方の主面及び前記ガス拡散層の一方の主面のそれぞれに形成されている、請求項1~9のいずれか1項に記載の高分子電解質形燃料電池。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/516,869 US8980500B2 (en) | 2010-02-05 | 2011-02-02 | Polymer electrolyte fuel cell comprising reactant gas channels overlapping a peripheral portion of an electrode |
| EP11739554.1A EP2533336B1 (en) | 2010-02-05 | 2011-02-02 | Polymer electrolyte fuel cell |
| CN201180005032.5A CN102959780B (zh) | 2010-02-05 | 2011-02-02 | 高分子电解质型燃料电池 |
| JP2011552692A JP5079146B2 (ja) | 2010-02-05 | 2011-02-02 | 高分子電解質形燃料電池 |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2010024372 | 2010-02-05 | ||
| JP2010-024372 | 2010-02-05 |
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| WO2011096205A1 true WO2011096205A1 (ja) | 2011-08-11 |
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| PCT/JP2011/000567 Ceased WO2011096205A1 (ja) | 2010-02-05 | 2011-02-02 | 高分子電解質形燃料電池 |
Country Status (5)
| Country | Link |
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| US (1) | US8980500B2 (ja) |
| EP (1) | EP2533336B1 (ja) |
| JP (1) | JP5079146B2 (ja) |
| CN (1) | CN102959780B (ja) |
| WO (1) | WO2011096205A1 (ja) |
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| EP2549573A4 (en) * | 2010-03-17 | 2015-07-01 | Panasonic Ip Man Co Ltd | POLYMER ELECTROLYTE FUEL CELL AND FUEL CELL STACK EQUIPPED WITH SAME |
| JP2018129274A (ja) * | 2017-02-10 | 2018-08-16 | パナソニックIpマネジメント株式会社 | 燃料電池 |
| WO2019198457A1 (ja) * | 2018-04-10 | 2019-10-17 | パナソニックIpマネジメント株式会社 | 燃料電池セルおよび燃料電池スタック |
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| CN109565066B (zh) * | 2016-08-26 | 2021-12-07 | 百拉得动力系统公司 | 具有改善的耐久性的燃料电池 |
| EP3547427A1 (en) * | 2018-03-28 | 2019-10-02 | Toyota Jidosha Kabushiki Kaisha | Fuel cell |
| JP7067363B2 (ja) | 2018-03-28 | 2022-05-16 | トヨタ自動車株式会社 | 燃料電池 |
| JP6586541B1 (ja) * | 2018-07-12 | 2019-10-02 | 日本碍子株式会社 | 電気化学セル、及びセルスタック装置 |
| FR3091416B1 (fr) * | 2019-01-02 | 2022-12-16 | Commissariat Energie Atomique | Plaque bipolaire a zone d’homogeneisation limitant les debits de court-circuit |
| DE102022209317A1 (de) * | 2022-09-07 | 2024-03-07 | Robert Bosch Gesellschaft mit beschränkter Haftung | Separatorplattenhälfte, Separatorplatte, Brennstoffzellensystem sowie Verfahren |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2533336A4 (en) | 2016-06-01 |
| JPWO2011096205A1 (ja) | 2013-06-10 |
| CN102959780B (zh) | 2015-03-11 |
| US8980500B2 (en) | 2015-03-17 |
| JP5079146B2 (ja) | 2012-11-21 |
| EP2533336A1 (en) | 2012-12-12 |
| CN102959780A (zh) | 2013-03-06 |
| EP2533336B1 (en) | 2017-11-08 |
| US20120258380A1 (en) | 2012-10-11 |
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