WO2010074005A1 - 燃料電池 - Google Patents
燃料電池 Download PDFInfo
- Publication number
- WO2010074005A1 WO2010074005A1 PCT/JP2009/071173 JP2009071173W WO2010074005A1 WO 2010074005 A1 WO2010074005 A1 WO 2010074005A1 JP 2009071173 W JP2009071173 W JP 2009071173W WO 2010074005 A1 WO2010074005 A1 WO 2010074005A1
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- WIPO (PCT)
- Prior art keywords
- catalyst layer
- anode
- cathode
- fuel
- fuel cell
- Prior art date
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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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/8626—Porous electrodes characterised by the form
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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
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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
-
- 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
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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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
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/242—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes comprising framed electrodes or intermediary frame-like gaskets
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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
- H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
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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
- This invention relates to a technology of a fuel cell using liquid fuel.
- DMFC Direct-Methanol-Fuel-Cell
- the DMFC includes a membrane-electrode assembly (hereinafter referred to as MEA) having an electrolyte membrane sandwiched between an anode and a cathode.
- MEA membrane-electrode assembly
- the introduced methanol is oxidatively decomposed to generate protons, electrons and carbon dioxide.
- oxygen in the air, protons moving from the anode side, and electrons supplied from the anode through an external circuit react to generate water. Also, power is supplied by electrons passing through an external circuit.
- the voltage generated by the DMFC is 1.21 V, which is lower than a general battery, in the cell voltage without reversible loss.
- the DMFC employs a technique in which a plurality of single cells are overlapped or arranged, and the single cells are connected in series to increase the voltage.
- a plurality of single cells are often arranged in parallel and connected in series by connecting an anode and a cathode with electrodes of metal conductors.
- a catalyst dropped from the anode catalyst layer or the cathode catalyst layer may cause a short circuit between adjacent anodes or cathodes, and a predetermined voltage may not be secured.
- the present invention has been made in view of the above-described problems, and an object thereof is to provide a fuel cell capable of preventing a short circuit between adjacent anodes or cathodes.
- a fuel cell includes an electrolyte membrane, an anode having a plurality of anode catalyst layers disposed on one surface of the electrolyte membrane at intervals, and an anode gas diffusion layer laminated on the anode catalyst layer.
- a fuel cell capable of preventing a short circuit between adjacent anodes or between cathodes can be provided.
- FIG. 1 is a cross-sectional view schematically showing the structure of a fuel cell according to an embodiment of the present invention.
- FIG. 2 is a perspective view schematically showing a cross section of a part of the MEA in the fuel cell shown in FIG.
- FIG. 3 is a plan view of the MEA shown in FIG. 4 is an enlarged cross-sectional view of a portion A shown in FIG.
- FIG. 5 is a diagram showing the separation distance of the anode catalyst layer and the separation distance of the cathode catalyst layer.
- FIG. 6 is a diagram showing a verification result of the effect of forming the inclined surface on the anode catalyst layer.
- FIG. 7 is a diagram showing a verification result of the effect of forming the cathode catalyst layer on the inclined surface.
- FIG. 8 is a cross-sectional view schematically showing another structure of the MEA of the fuel cell according to the present embodiment.
- FIG. 9 is a cross-sectional view schematically showing another structure of the MEA of the fuel cell
- the fuel cell 1 mainly includes an MEA 2 that constitutes an electromotive unit, and a fuel supply mechanism 3 that supplies fuel to the MEA 2.
- the MEA 2 includes an anode catalyst layer 11 and an anode (or a fuel electrode) 13 having an anode gas diffusion layer 12 disposed on the anode catalyst layer 11, a cathode catalyst layer 14, and a cathode catalyst.
- An electrolyte membrane 17 is provided.
- Examples of the catalyst contained in the anode catalyst layer 11 and the cathode catalyst layer 14 include platinum such as platinum (Pt), ruthenium (Ru), rhodium (Rh), iridium (Ir), osmium (Os), and palladium (Pd). Examples thereof include a group element simple substance and an alloy containing a platinum group element.
- platinum platinum
- Ru ruthenium
- Rh rhodium
- Ir iridium
- Os osmium
- Pd palladium
- Examples thereof include a group element simple substance and an alloy containing a platinum group element.
- Pt—Ru, Pt—Mo, or the like that has strong resistance to methanol, carbon monoxide, or the like.
- Pt, Pt—Ni, or the like is preferably used for the cathode catalyst layer 14.
- the catalyst is not limited to these, and various substances having catalytic activity can be used.
- the catalyst may be either a supported catalyst using a
- the anode catalyst layer 11 and the cathode catalyst layer 14 have, for example, fluorine-based resins such as perfluorosulfonic acid polymer (Nafion (trade name, manufactured by DuPont), Flemion (trade name, Asahi Glass Co., Ltd.) having a sulfonic acid group. Or the like), a hydrocarbon resin having a sulfonic acid group, or a proton conductive agent such as an inorganic substance such as tungstic acid, phosphotungstic acid, or lithium nitrate.
- fluorine-based resins such as perfluorosulfonic acid polymer (Nafion (trade name, manufactured by DuPont), Flemion (trade name, Asahi Glass Co., Ltd.) having a sulfonic acid group. Or the like), a hydrocarbon resin having a sulfonic acid group, or a proton conductive agent such as an inorganic substance such as tungstic acid, phospho
- Examples of the proton conductive material constituting the electrolyte membrane 17 include fluorine-based resins (Nafion (trade name, manufactured by DuPont) and Flemion (trade name, manufactured by Asahi Glass Co., Ltd.) such as a perfluorosulfonic acid polymer having a sulfonic acid group. Etc.), organic materials such as hydrocarbon resins having sulfonic acid groups, or inorganic materials such as tungstic acid and phosphotungstic acid.
- fluorine-based resins Nafion (trade name, manufactured by DuPont) and Flemion (trade name, manufactured by Asahi Glass Co., Ltd.)
- organic materials such as hydrocarbon resins having sulfonic acid groups
- inorganic materials such as tungstic acid and phosphotungstic acid.
- the proton conductive electrolyte membrane 17 is not limited to these.
- the anode gas diffusion layer 12 laminated on the anode catalyst layer 11 serves to uniformly supply fuel to the anode catalyst layer 11 and has a current collecting function of the anode catalyst layer 11.
- the cathode gas diffusion layer 15 laminated on the cathode catalyst layer 14 serves to uniformly supply an oxidant (for example, oxygen contained in air) to the cathode catalyst layer 14 and at the same time, collects electricity of the cathode catalyst layer 14. It is what has.
- the anode gas diffusion layer 12 and the cathode gas diffusion layer 15 are made of a porous substrate having conductivity such as carbon paper.
- the MEA 2 is sealed by a seal member 19 such as a rubber O-ring disposed on the anode 13 side and the cathode 16 side of the electrolyte membrane 17, thereby preventing fuel leakage and oxidant leakage from the MEA 2. ing.
- a seal member 19 such as a rubber O-ring disposed on the anode 13 side and the cathode 16 side of the electrolyte membrane 17, thereby preventing fuel leakage and oxidant leakage from the MEA 2. ing.
- a plate-like body 20 made of an insulating material is disposed on the cathode 16 side of the MEA 2.
- This plate-like body 20 mainly functions as a moisture retaining layer. That is, the plate-like body 20 is impregnated with a part of the water generated in the cathode catalyst layer 14 to suppress the transpiration of water, adjusts the amount of air taken into the cathode catalyst layer 14 and makes the air uniform. Promotes diffusion.
- the plate-like body 20 is constituted by, for example, a member having a porous structure, and specific constituent materials include polyethylene and polypropylene porous bodies.
- the above-described MEA 2 is disposed between the fuel supply mechanism 3 and the cover plate 21.
- the cover plate 21 has a substantially rectangular appearance, and is made of, for example, stainless steel (SUS). Further, the cover plate 21 has a plurality of openings 21A for taking in air as an oxidant.
- the fuel supply mechanism 3 is configured to supply fuel to the anode 13 of the MEA 2, but is not particularly limited to a specific configuration. Hereinafter, an example of the fuel supply mechanism 3 will be described.
- the fuel supply mechanism 3 includes a container 30 formed in a box shape, for example.
- the fuel supply mechanism 3 is connected to a fuel storage unit 4 that stores liquid fuel via a flow path 5.
- the container 30 has a fuel inlet 30A, and the fuel inlet 30A and the flow path 5 are connected.
- the container 30 is constituted by a resin container, for example. As a material for forming the container 30, a material having resistance to liquid fuel is selected.
- the fuel supply mechanism 3 includes a fuel supply unit 31 that supplies fuel while dispersing and diffusing the fuel in the surface direction of the anode 13 of the MEA 2.
- a fuel supply unit 31 that supplies fuel while dispersing and diffusing the fuel in the surface direction of the anode 13 of the MEA 2.
- the fuel supply unit 31 may have other configurations.
- the fuel distribution plate 31A has one fuel injection port 32 and a plurality of fuel discharge ports 33, and the fuel injection port 32 and the fuel discharge port 33 are connected to each other through a fuel passage such as a narrow tube 34. It is a connected configuration.
- the fuel inlet 32 is in communication with the fuel inlet 30A of the container 30.
- the fuel inlet 32 of the fuel distribution plate 31 ⁇ / b> A is connected to the fuel storage portion 4 via the flow path 5.
- the fuel discharge ports 33 are at, for example, 128 locations, and discharge liquid fuel or its vaporized components.
- the liquid fuel injected from the fuel injection port 32 is guided to a plurality of fuel discharge ports 33 through a plurality of thin tubes 34.
- a fuel distribution plate 31A By using such a fuel distribution plate 31A, the liquid fuel injected from the fuel injection port 32 can be evenly distributed to the plurality of fuel discharge ports 33 regardless of the direction or position. Therefore, it is possible to further increase the uniformity of the power generation reaction in the plane of the MEA 2.
- the MEA 2 is arranged so that its anode 13 faces the fuel discharge port 33 of the fuel distribution plate 31A as described above.
- the cover plate 21 is fixed to the container 30 by a method such as caulking or screwing while holding the MEA 2 between the cover plate 21 and the fuel supply mechanism 3. Thereby, the power generation unit of the fuel cell (DMFC) 1 is configured.
- the fuel supply unit 31 is desirably configured to form a space functioning as a fuel diffusion chamber 31B between the fuel distribution plate 31A and the MEA 2.
- the fuel diffusion chamber 31 ⁇ / b> B has a function of promoting vaporization and promoting diffusion in the surface direction even when liquid fuel is discharged from the fuel discharge port 33.
- a supporting member that supports the MEA 2 from the anode 13 side may be disposed between the MEA 2 and the fuel supply unit 31.
- At least one porous body may be disposed between the MEA 2 and the fuel supply unit 31.
- the fuel storage unit 4 stores liquid fuel corresponding to the MEA 2.
- the liquid fuel include methanol fuels such as aqueous methanol solutions of various concentrations and pure methanol.
- the liquid fuel is not necessarily limited to methanol fuel.
- the liquid fuel may be, for example, an ethanol fuel such as an ethanol aqueous solution or pure ethanol, a propanol fuel such as a propanol aqueous solution or pure propanol, a glycol fuel such as a glycol aqueous solution or pure glycol, dimethyl ether, formic acid, or other liquid fuel.
- the fuel storage unit 4 stores liquid fuel corresponding to the MEA 2.
- a pump 6 may be interposed in the flow path 5.
- the pump 6 is not a circulation pump that circulates fuel, but is a fuel supply pump that sends liquid fuel from the fuel storage unit 4 to the fuel supply unit 31 to the last.
- the fuel supplied from the fuel supply unit 31 to the MEA 2 is used for a power generation reaction, and is not circulated thereafter and returned to the fuel storage unit 4.
- the fuel cell 1 of this embodiment is different from the conventional active method because it does not circulate the fuel, and does not impair the downsizing of the device. Further, the pump 6 is used to supply the liquid fuel, which is different from a pure passive system such as a conventional internal vaporization type.
- the fuel cell 1 shown in FIG. 1 employs a system called a semi-passive type, for example.
- liquid fuel is intermittently sent from the fuel storage unit 4 to the fuel supply unit 31 using the pump 6.
- the liquid fuel fed by the pump 6 is uniformly supplied to the entire surface of the anode 13 of the MEA 2 through the fuel supply unit 31.
- the fuel is uniformly supplied to the planar direction of each anode 13 of the plurality of single cells C, thereby generating a power generation reaction.
- the operation of the fuel supply pump 6 is preferably controlled based on the output of the fuel cell 1, temperature information, operation information of an electronic device that is a power supply destination, and the like.
- the fuel released from the fuel supply unit 31 is supplied to the anode 13 of the MEA 2.
- the fuel diffuses through the anode gas diffusion layer 12 and is supplied to the anode catalyst layer 11.
- an internal reforming reaction of methanol shown in the following formula (1) occurs in the anode catalyst layer 11.
- pure methanol is used as the methanol fuel
- the water generated in the cathode catalyst layer 14 or the water in the electrolyte membrane 17 is reacted with methanol to cause the internal reforming reaction of the formula (1).
- the internal reforming reaction is caused by another reaction mechanism that does not require water.
- Electrons (e ⁇ ) generated by this reaction are guided to the outside via a current collector, and after operating a portable electronic device or the like as so-called electricity, they are guided to the cathode 16 via the current collector. .
- Proton (H + ) generated by the internal reforming reaction of the formula (1) is guided to the cathode 16 through the electrolyte membrane 17. Air is supplied to the cathode 16 as an oxidant.
- Electrons (e ⁇ ) and protons (H + ) reaching the cathode 16 react with oxygen in the air in the cathode catalyst layer 14 in accordance with the following equation (2), and water is generated along with this reaction.
- the MEA 2 includes a plurality of anodes 13 arranged at intervals on one surface of a single electrolyte membrane 17, and the electrolyte membrane 17. And a plurality of cathodes 16 arranged at intervals so as to face each of the anodes 13 on the other surface.
- a case where there are four anodes 13 and four cathodes 16 is shown.
- Each combination of the anode 13 and the cathode 16 sandwiches the electrolyte membrane 17 to form a single cell C (C1, C2, C3, C4).
- each of the single cells C (C1, C2, C3, C4) is arranged side by side in the direction D perpendicular to the longitudinal direction on the same plane.
- the structure of the MEA 2 is not limited to this example, and may be another structure.
- each single cell C (C 1, C 2, C 3, C 4) is separated by a current collector 18. They are electrically connected in series.
- the current collector 18 has an anode current collector 18A and a cathode current collector 18C as shown in FIG.
- the current collector 18 has four anode current collectors 18A and cathode current collectors 18C, respectively.
- Each of the anode current collectors 18A is laminated on the anode gas diffusion layer 12 in each single cell C (C1, C2, C3, C4).
- Each of the cathode current collectors 18C is stacked on the cathode gas diffusion layer 15 in each single cell C (C1, C2, C3, C4).
- a porous film for example, a mesh
- a foil body made of a metal material such as gold (Au) or nickel (Ni), or a conductive material such as stainless steel (SUS).
- a composite material obtained by coating a conductive metal material with a good conductive metal such as gold can be used.
- the thickness of at least one of the anode catalyst layer 11 and the cathode catalyst layer 14 becomes thinner toward the outside.
- each of the anode catalyst layer 11 and the cathode catalyst layer 14 of the single cell C is formed so as to have a trapezoidal cross section in which the thickness of the end portion is gradually reduced.
- the anode catalyst layer 11 and the cathode catalyst layer 14 are tapered so that the area of the upper surface is smaller than the bottom surface in contact with the electrolyte membrane 17.
- the area of the bottom surface 11B1 of the anode catalyst layer 11 in contact with the electrolyte membrane 17 is larger than the area of the top surface 11B2 of the anode catalyst layer 11 in contact with the anode gas diffusion layer 12.
- the anode catalyst layer 11 has a side surface 11a that connects the bottom surface 11B1 and the top surface 11B2. Opposing side surfaces 11a of adjacent anode catalyst layers 11 are inclined surfaces.
- the anode gas diffusion layer 12 has a side surface 12a that connects the bottom surface 12B1 and the top surface 12B2.
- the side surface 12 a is an inclined surface connected to the side surface 11 a of the anode catalyst layer 11.
- the inclination angle ⁇ 1 between the bottom surface 11B1 and the side surface 11a of the anode catalyst layer 11 is the same as the inclination angle ⁇ 2 between the bottom surface 12B1 and the side surface 12a of the anode gas diffusion layer 12, and both are acute angles.
- the area of the bottom surface 14B1 in contact with the electrolyte membrane 17 of the cathode catalyst layer 14 is larger than the area of the top surface 14B2 in contact with the cathode gas diffusion layer 15 of the cathode catalyst layer 14.
- the cathode catalyst layer 14 has a side surface 14a that connects the bottom surface 14B1 and the top surface 14B2. Opposing side surfaces 14a of adjacent cathode catalyst layers 14 are inclined surfaces.
- the cathode gas diffusion layer 15 has a side surface 15a that connects the bottom surface 15B1 and the top surface 15B2.
- the side surface 15 a is an inclined surface connected to the side surface 14 a of the cathode catalyst layer 14.
- the inclination angle ⁇ 3 between the bottom surface 14B1 and the side surface 14a of the cathode catalyst layer 14 is the same as the inclination angle ⁇ 4 between the bottom surface 15B1 and the side surface 15a of the cathode gas diffusion layer 15, and both are acute angles.
- the thickness of the anode catalyst layer 11 of one unit cell C2 becomes thinner toward the other unit cell C3. That is, the side surface 11a formed along the side L2 facing the anode catalyst layer 11 of the single cell C3 in the anode catalyst layer 11 of the single cell C2 is an inclined surface. Similarly, the side surface 11a formed along the side L3 facing the anode catalyst layer 11 of the single cell C2 in the anode catalyst layer 11 of the single cell C3 is also an inclined surface. In each single cell C, the side surfaces 11a of the anode catalyst layers 11 facing each other are inclined surfaces.
- the thickness of the cathode catalyst layer 14 of one unit cell C2 becomes thinner toward the other unit cell C3. That is, the side surface 14a formed along the side L2 facing the cathode catalyst layer 14 of the single cell C3 in the cathode catalyst layer 14 of the single cell C2 is an inclined surface. Similarly, the side surface 14a formed along the side L3 facing the cathode catalyst layer 14 of the single cell C2 in the cathode catalyst layer 14 of the single cell C3 is also an inclined surface. In each single cell C, the side surfaces 14a of the cathode catalyst layers 14 facing each other are inclined surfaces.
- the side surface 11a of the anode catalyst layer 11 and the side surface 14a of the cathode catalyst layer 14 that do not face each other need not be inclined surfaces.
- the side surface along the side S2 that is not adjacent to the single cell C1 and the single cell C3 of the single cell C2 may not be an inclined surface.
- the side surfaces facing the outside of the single cells C1 and C4 may not be inclined surfaces.
- the side surface 11a of the anode catalyst layer 11 and the side surface 14a of the cathode catalyst layer 14 are gently inclined surfaces, so that it is possible to prevent the catalyst from falling off from the anode catalyst layer 11 and the cathode catalyst layer 14. Become. Further, since the side surfaces 11a of the anode catalyst layers 11 adjacent to each other are inclined surfaces, it is possible to prevent the catalyst from dropping between the anode catalyst layers 11. Further, since the side surfaces 14a facing each other of the cathode catalyst layers 14 adjacent to each other are inclined surfaces, it is possible to prevent the catalyst from falling off between the cathode catalyst layers 14.
- the anode catalyst layer 11 of one adjacent single cell is configured to become thinner toward the other single cell. Further, in order to prevent only the catalyst from dropping off in the cathode catalyst layer 14, the cathode catalyst layer 14 of one adjacent single cell is configured to become thinner toward the other single cell.
- the inclination angle ⁇ 1 of the anode catalyst layer 11 and the inclination angle ⁇ 3 of the cathode catalyst layer 14 have optimum angles.
- the optimum angles of the inclination angle ⁇ 1 of the anode catalyst layer 11 and the inclination angle ⁇ 3 of the cathode catalyst layer 14 are 30 ° or more and 80 ° or less.
- carbon paper (TGP-H-030-120 manufactured by Toray Industries, Inc.) for the anode gas diffusion layer 12 was prepared.
- the carbon paper was compressed with a flat plate press in the thickness direction until the thickness became 1/2.
- the porosity of the carbon paper before compression was 75% as measured by Archimedes method.
- the porosity after compression of the carbon paper was 40.5% as calculated from the external dimensions and weight measurement.
- Nafion solution DE2020 manufactured by DuPont
- carbon particles carrying platinum ruthenium alloy fine particles as a catalyst
- a solvent is added and mixed with a homogenizer.
- a slurry was applied on the anode gas diffusion layer 12 by the die coater spray coating method and dried to form the anode catalyst layer 11. Thereby, the anode 13 was obtained.
- carbon paper (TGP-H-60 manufactured by Toray Industries, Inc.) for the cathode gas diffusion layer 15 was prepared. At this time, the porosity of the carbon paper was 75%.
- the anode 13 and the cathode 16 were each cut into a predetermined size with a cutter knife. At this time, the anode 13 and the cathode 16 were cut using a cutter knife having blades of various angles so that the angle of the cut surface was changed.
- the inclination angle ⁇ 1 of the anode catalyst layer 11 and the inclination angle ⁇ 3 of the cathode catalyst layer 14 can be measured by observing the cut surface at 10 to 100 times and performing a cross-sectional analysis.
- a fixed electrolyte membrane Nafion 112 (manufactured by DuPont) is used as the electrolyte membrane 17, and the electrolyte membrane 17 and the cathode 16 are first overlapped so that the cathode catalyst layer 14 faces the electrolyte membrane 17 side.
- the anode 13 is overlaid on the surface of the electrolyte membrane 17 opposite to the surface on which the cathode 16 is overlaid so that the anode catalyst layer 11 faces the electrolyte membrane 17 side.
- pressing was performed under the conditions of a temperature of 150 ° C. and a pressure of 30 kgf / cm 2 to form MEA2.
- the electrode area was 8 cm 2 of 1 cm ⁇ 8 cm for both the anode 13 and the cathode 16.
- the anode 13 and the cathode 16 were arranged in four rows at 1.2 mm intervals.
- MEA 2 was sandwiched between gold foils functioning as a current collector 18 having a plurality of openings for taking in air and vaporized methanol to form an anode current collector 18A and a cathode current collector 18C.
- the frame on the anode 13 side was fixed to the fuel supply mechanism 3 with screws through a gas-liquid separation membrane.
- a gas-liquid separation membrane a silicone sheet having a thickness of 0.1 mm was used.
- a plate-like body 20 functioning as a moisture retention layer having a porosity of 30% was disposed on the frame on the cathode 16 side.
- a stainless steel plate (SUS304) having a thickness of 2 mm in which an opening 21 ⁇ / b> A for taking in air is formed is arranged as a cover plate 21 and fixed by screwing.
- the aperture 21A has a diameter of 4 mm.
- the number of openings 21A is 64. In this way, the fuel cell 1 was assembled.
- Pure methanol was injected into the fuel storage chamber of such a fuel cell 1.
- the fuel cell 1 was operated for 500 hours in an environment of a temperature of 25 ° C. and a relative humidity of 50%.
- the MEA 2 after 500 hours of operation is taken out and observed. Further, the separation distance L of the anode catalyst layer 11 of the fuel cell 1 including the samples A1 to A5 and A6, and the cathode catalyst layer 14 of the fuel cell 1 including the samples B1 to B6 are observed.
- the peel distance L was measured.
- the separation distance L of the anode catalyst layer 11 is the distance between the end of the bottom surface of the anode catalyst layer 11 and the catalyst that has fallen to the farthest position from the anode catalyst layer 11.
- the separation distance L of the cathode catalyst layer 14 is the distance between the end of the bottom surface of the cathode catalyst layer 14 and the catalyst that has fallen to the farthest position from the cathode catalyst layer 14.
- the state on the anode 13 side when the MEA 2 is formed is as follows.
- sample A1 it was confirmed that the catalyst was removed from the anode catalyst layer 11, and peeling of the anode catalyst layer 11 was confirmed.
- Samples A2 to A5 the anode catalyst layer 11 did not peel off, and the catalyst did not fall off from the anode catalyst layer 11.
- sample A6 it was confirmed that the catalyst was removed from the anode catalyst layer 11, and peeling of the anode catalyst layer 11 was confirmed.
- peeling of the anode catalyst layer 11 means that a part of the anode catalyst layer 11 is peeled off from the electrolyte membrane 17 or the anode gas diffusion layer 12.
- the state on the cathode 16 side when the MEA 2 is formed is as follows.
- sample B1 it was confirmed that the catalyst was removed from the cathode catalyst layer 14, and peeling of the cathode catalyst layer 14 was confirmed.
- Samples B2 to B5 the cathode catalyst layer 14 was not peeled off, and the catalyst was not detached from the cathode catalyst layer 14.
- sample B6 it was confirmed that the catalyst was removed from the cathode catalyst layer 14, and peeling of the cathode catalyst layer 14 was confirmed.
- peeling of the cathode catalyst layer 14 means that a part of the cathode catalyst layer 14 is peeled off from the electrolyte membrane 17 or the cathode gas diffusion layer 15.
- the state on the anode 13 side after the fuel cell 1 is operated for 500 hours is as follows.
- the catalyst dropping from the anode catalyst layer 11 increased from the initial stage.
- the anode catalyst layer 11 was somewhat peeled off, and the catalyst was slightly removed from the anode catalyst layer 11.
- the anode catalyst layer 11 was not peeled off, and the catalyst was not detached from the anode catalyst layer 11.
- the catalyst dropping from the anode catalyst layer 11 increased from the initial stage.
- the state on the cathode 16 side after the fuel cell 1 is operated for 500 hours is as follows.
- sample B1 the catalyst dropping from the cathode catalyst layer 14 increased from the initial stage.
- sample B2 the cathode catalyst layer 14 was slightly peeled off, and the catalyst was slightly removed from the cathode catalyst layer 14.
- Sample B3 and Sample B4 the cathode catalyst layer 14 did not peel off, and the catalyst did not fall off from the cathode catalyst layer 14.
- the cathode catalyst layer 14 was slightly peeled off, and the catalyst was slightly removed from the cathode catalyst layer 14.
- sample B6 the catalyst dropped from the cathode catalyst layer 14 increased from the initial stage.
- the interval between the adjacent anode 13 and the cathode 16 is 1.2 mm, when the separation distance L of the catalyst is less than 0.2 mm, there is no short circuit between the adjacent anode 13 and the cathode 16. Furthermore, even if the fuel cell 1 is continuously operated, the possibility of a short circuit is very low. 6 and 7, the evaluation when the peeling distance L is less than 0.1 mm is “ ⁇ ”, and the evaluation when the peeling distance L is 0.1 mm or more and less than 0.2 mm is “ ⁇ ⁇ ”. .
- the peel distance L is 0.4 mm or more and less than 0.6 mm, there is a low possibility of short-circuiting between the adjacent anodes 13 and between the cathodes 16, but there is a possibility of short-circuiting if the fuel cell 1 is further operated. 6 and 7, the evaluation when the peeling distance L is 0.4 mm or more is “x”.
- the peel distance L was 0.25 mm, and the evaluation was “ ⁇ ”.
- the peel distance L was 0.1 mm, and the evaluation was “ ⁇ ⁇ ”.
- the peel distance L was 0.05 mm or less, and the evaluation was “ ⁇ ”.
- the peel distance L was 0.05 mm or less, and the evaluation was “ ⁇ ”.
- the peel distance L was 0.2 mm, and the evaluation was “ ⁇ ”.
- the separation distance L of the anode catalyst layer 11 becomes small. That is, the inclination angle ⁇ 1 of the anode catalyst layer 11 is desirably 30 ° to 80 °, and more desirably 45 ° to 75 °.
- sample B1 the peel distance L was 0.3 mm, and the evaluation was “ ⁇ ”.
- sample B2 the peel distance L was 0.15 mm, and the evaluation was “ ⁇ ⁇ ”.
- sample B3 the peel distance L was 0.05 mm or less, and the evaluation was “ ⁇ ”.
- sample B4 the peel distance L was 0.1 mm, and the evaluation was “ ⁇ ⁇ ”.
- sample B5 the peel distance L was 0.25 mm, and the evaluation was “ ⁇ ”.
- the separation distance L of the cathode catalyst layer 14 becomes small. That is, the inclination angle ⁇ 3 of the cathode catalyst layer 14 is desirably 30 ° or more and 80 ° or less, and more desirably 45 ° or more and 75 ° or less.
- the fuel cell 1 capable of preventing a short circuit between the adjacent anode 13 and cathode 16.
- the inclination angle ⁇ 1 of the side surface 11a of the anode catalyst layer 11 and the inclination angle ⁇ 2 of the side surface 12a of the anode gas diffusion layer 12 may be different ( ⁇ 1 ⁇ ⁇ 2).
- the inclination angle ⁇ 3 of the side surface 14a of the cathode catalyst layer 14 and the inclination angle ⁇ 4 of the side surface 15a of the cathode gas diffusion layer 15 may be different ( ⁇ 3 ⁇ ⁇ 4).
- the above-described fuel cell 1 of the present embodiment is effective when various liquid fuels are used, and the type and concentration of the liquid fuel are not limited.
- the fuel supply unit 31 that supplies fuel while being dispersed in the plane direction is particularly effective when the fuel concentration is high.
- the fuel cell 1 of each embodiment can exhibit its performance and effects particularly when methanol having a concentration of 80 wt% or more is used as the liquid fuel. Therefore, each embodiment is suitable for the fuel cell 1 using a methanol aqueous solution having a methanol concentration of 80 wt% or more or pure methanol as a liquid fuel.
- the present invention can be applied to various fuel cells using liquid fuel.
- the specific configuration of the fuel cell, the supply state of the fuel, and the like are not particularly limited, and all of the fuel supplied to the MEA is liquid fuel vapor, all is liquid fuel, or part is liquid state.
- the present invention can be applied to various forms such as a vapor of supplied liquid fuel.
- the constituent elements can be modified and embodied without departing from the technical idea of the present invention.
- various modifications are possible, such as appropriately combining a plurality of constituent elements shown in the above embodiment, or deleting some constituent elements from all the constituent elements shown in the embodiment.
- Embodiments of the present invention can be expanded or modified within the scope of the technical idea of the present invention, and these expanded and modified embodiments are also included in the technical scope of the present invention.
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Abstract
Description
この反応で生成した電子(e-)は、集電体を経由して外部に導かれ、いわゆる電気として携帯用電子機器等を動作させた後、集電体を経由してカソード16に導かれる。(1)式の内部改質反応で生成したプロトン(H+)は、電解質膜17を経てカソード16に導かれる。カソード16には、酸化剤として空気が供給される。カソード16に到達した電子(e-)とプロトン(H+)は、カソード触媒層14で空気中の酸素と下記の(2)式にしたがって反応し、この反応に伴って水が生成する。
上述した燃料電池1の発電反応において、発電する電力を増大させるためには触媒反応を円滑に行わせるとともに、MEA2の電極全体に均一に燃料を供給し、電極全体をより有効に発電に寄与させることが重要となる。
Claims (7)
- 電解質膜と、
前記電解質膜の一方の面に間隔をおいて配置された複数のアノード触媒層及び前記アノード触媒層に積層されたアノードガス拡散層を有するアノードと、
前記電解質膜の他方の面に前記アノード触媒層のそれぞれと対向するように間隔をおいて配置された複数のカソード触媒層及び前記カソード触媒層に積層されたカソードガス拡散層を有するカソードと、によって構成された複数の単セルを備えた膜電極接合体を備え、
隣接する一方の単セルの前記アノード触媒層及び前記カソード触媒層の少なくとも一方の厚さは、他方の単セルに向かうにしたがって薄くなることを特徴とする燃料電池。 - 前記アノード触媒層の前記電解質膜に接する底面の面積は、前記アノード触媒層の前記アノードガス拡散層に接する上面の面積より大きいことを特徴とする請求項1に記載の燃料電池。
- 前記アノード触媒層の前記底面と前記上面とを接続する側面を有し、
隣接する前記アノード触媒層の互いに向かい合う前記側面は、それぞれ傾斜面であることを特徴とする請求項2に記載の燃料電池。 - 前記アノード触媒層の前記底面と前記側面との間の傾斜角度は、30°以上80°以下であることを特徴とする請求項3に記載の燃料電池。
- 前記カソード触媒層の前記電解質膜に接する底面の面積は、前記カソード触媒層の前記カソードガス拡散層に接する上面の面積より大きいことを特徴とする請求項1に記載の燃料電池。
- 前記カソード触媒層は、前記底面と前記上面とを接続する側面を有し、
隣接する前記カソード触媒層の互いに向かい合う前記側面は、それぞれ傾斜面であることを特徴とする請求項5に記載の燃料電池。 - 前記カソード触媒層の前記底面と前記側面との間の傾斜角度は、30°以上80°以下であることを特徴とする請求項6に記載の燃料電池。
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CN2009801529166A CN102265444A (zh) | 2008-12-26 | 2009-12-18 | 燃料电池 |
US13/165,323 US8304132B2 (en) | 2008-12-26 | 2011-06-21 | Fuel cell |
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JP2008334003A JP2010157390A (ja) | 2008-12-26 | 2008-12-26 | 燃料電池 |
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US (1) | US8304132B2 (ja) |
JP (1) | JP2010157390A (ja) |
KR (1) | KR20110094082A (ja) |
CN (1) | CN102265444A (ja) |
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Cited By (2)
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WO2012035591A1 (ja) * | 2010-09-16 | 2012-03-22 | トヨタ自動車株式会社 | 膜電極接合体およびそれを用いた燃料電池、膜電極接合体の製造方法 |
CN103493270A (zh) * | 2011-04-20 | 2014-01-01 | 日本特殊陶业株式会社 | 燃料电池单元及燃料电池 |
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GB2529149A (en) * | 2014-08-04 | 2016-02-17 | Intelligent Energy Ltd | Fuel cell |
JP6055007B2 (ja) * | 2015-03-10 | 2016-12-27 | 本田技研工業株式会社 | 膜電極接合体の製造方法 |
WO2017072898A1 (ja) * | 2015-10-29 | 2017-05-04 | 株式会社豊田自動織機 | 電極組立体、及び電極組立体の製造方法 |
CN111989810B (zh) * | 2018-03-30 | 2023-10-27 | 本田技研工业株式会社 | 燃料电池 |
DE102018221338A1 (de) * | 2018-12-10 | 2020-06-10 | Robert Bosch Gmbh | Elektrodenstapel für eine galvanische Zelle |
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- 2009-12-18 WO PCT/JP2009/071173 patent/WO2010074005A1/ja active Application Filing
- 2009-12-18 CN CN2009801529166A patent/CN102265444A/zh active Pending
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CN102265444A (zh) | 2011-11-30 |
TW201041215A (en) | 2010-11-16 |
KR20110094082A (ko) | 2011-08-19 |
US20110275001A1 (en) | 2011-11-10 |
US8304132B2 (en) | 2012-11-06 |
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