WO2010073900A1 - Electrode anodique pour pile à combustible à méthanol direct, et complexe membrane-électrode et pile à combustible l'utilisant - Google Patents

Electrode anodique pour pile à combustible à méthanol direct, et complexe membrane-électrode et pile à combustible l'utilisant Download PDF

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Publication number
WO2010073900A1
WO2010073900A1 PCT/JP2009/070494 JP2009070494W WO2010073900A1 WO 2010073900 A1 WO2010073900 A1 WO 2010073900A1 JP 2009070494 W JP2009070494 W JP 2009070494W WO 2010073900 A1 WO2010073900 A1 WO 2010073900A1
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layer
anode
fuel cell
fuel
hydrophilic
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PCT/JP2009/070494
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English (en)
Japanese (ja)
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義彦 中野
武 梅
淳 田村
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株式会社 東芝
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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
    • H01M8/1009—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]
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • 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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0243—Composites in the form of mixtures
    • 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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0245—Composites in the form of layered or coated products
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • 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 an anode electrode for a direct methanol fuel cell, a membrane electrode assembly using the anode electrode, and a fuel cell.
  • methanol is oxidatively decomposed at the fuel electrode to generate carbon dioxide, protons and electrons.
  • air electrode water is generated by oxygen obtained from air, protons supplied from the fuel electrode through the electrolyte membrane, and electrons supplied from the fuel electrode through an external circuit. Electric power is supplied by electrons passing through the external circuit.
  • DMFC is equipped with a pump for supplying methanol and a blower for supplying air as auxiliary devices.
  • a pump for supplying methanol and a blower for supplying air as auxiliary devices.
  • the system becomes complicated, and it is difficult to reduce the size of the DMFC having such a structure.
  • a small DMFC (passive DMFC) was constructed as follows. First, the fuel pump was made smaller by increasing the concentration of the fuel used. For intake of air, an air inlet directly attached to the power generation element was installed without using a blower. Due to the use of high concentration fuel, methanol crossover is large. Therefore, it is difficult for this passive DMFC to obtain a high output as compared with a normal active DMFC in which a low concentration fuel is used.
  • an anode diffusion comprising a conductive porous body, a hydrophilic polymer layer impregnated on one side of the conductive porous body, and a hydrophobic polymer layer impregnated on the other side of the conductive porous body It has been proposed to increase the output by using layers (see, for example, Patent Document 1).
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide an anode from which a high-power direct methanol fuel cell can be obtained.
  • An anode includes an anode catalyst layer, A first fuel diffusion layer provided on the anode catalyst layer; And a hydrophilic conductive layer provided on the first fuel diffusion layer and having a coating film containing conductive particles and a hydrophilic polymer.
  • a membrane electrode assembly includes the above-described anode, cathode, and a polymer electrolyte membrane disposed between the anode and the cathode.
  • a direct methanol fuel cell according to one embodiment of the present invention includes the above-described membrane electrode assembly and is supplied with liquid fuel.
  • an anode from which a high output fuel cell can be obtained is provided.
  • FIG. 1 is a cross-sectional view of a passive fuel cell according to an embodiment.
  • a fuel electrode (anode) 32, an air electrode (cathode) 33, and a polymer electrolyte membrane 15 sandwiched between them are provided.
  • a membrane electrode assembly (MEA: Electrode Assembly) 18 is used as an electromotive unit.
  • the polymer electrolyte membrane 15 has proton (hydrogen ion) conductivity.
  • the fuel electrode (anode) catalyst layer 11 is provided in contact with the polymer electrolyte membrane 15, and the first fuel diffusion layer 12 and the hydrophilic conductive layer 13 are sequentially disposed thereon.
  • the second fuel diffusion layer 14 is provided on the hydrophilic conductive layer 13, but the second fuel diffusion layer is not always essential.
  • an air electrode (cathode) catalyst layer 16 is provided in contact with the polymer electrolyte membrane 15, and an air electrode gas (cathode) diffusion layer 17 is disposed thereon.
  • the polymer electrolyte membrane 15 is made of a proton conductive material, and for example, a resin having a sulfonic acid group can be used.
  • a resin having a sulfonic acid group can be used.
  • fluororesin such as perfluorosulfonic acid polymer (Nafion (trade name, manufactured by DuPont), Flemion (trade name, manufactured by Asahi Glass), etc.
  • hydrocarbon-based resin having sulfonic acid group tungsten
  • tungsten examples thereof include inorganic substances such as acid and phosphotungstic acid, but are not limited thereto.
  • Examples of the catalyst contained in the anode catalyst layer 11 and the cathode catalyst layer 16 include platinum group elements such as Pt, Ru, Rh, Ir, Os, and Pd. Such a platinum group element can be used as a single metal. Alternatively, an alloy containing a platinum group element may be used as a catalyst. Specifically, for the anode catalyst layer 11, Pt—Ru, Pt—Mo or the like having strong resistance to methanol or carbon monoxide is preferably used.
  • the cathode catalyst layer 13 is preferably made of platinum or Pt—Ni, but is not limited thereto. Furthermore, a supported catalyst using a conductive support such as a carbon material or an unsupported catalyst may be used.
  • the catalyst is supported on the anode catalyst layer 11 and the cathode catalyst layer 16 in an amount of at least about 0.1 mg / cm 2 .
  • the amount of the catalyst supported on the anode catalyst layer 11 and the cathode catalyst layer 16 be limited to about 4 g / cm 2 .
  • the first fuel diffusion layer 12 laminated on the anode catalyst layer 11 serves to supply fuel to the anode catalyst layer 11 uniformly.
  • the first fuel diffusion layer 12 can be formed using any porous material having conductivity. It is also required that an anode catalyst layer can be formed on the first fuel diffusion layer 12 by coating or sputtering. Specific examples of materials that can be used for the first fuel diffusion layer 12 include, but are not limited to, porous carbon materials such as carbon paper and carbon cloth.
  • the first fuel diffusion layer 12 can have a microporous layer made of carbon nanofibers (CNF), carbon nanotubes (CNT) or nanocarbon particles on the anode catalyst layer 11 side.
  • CNF carbon nanofibers
  • CNT carbon nanotubes
  • the hydrophilic conductive layer 13 laminated on the first fuel diffusion layer 12 has an action of adjusting the amount of methanol supplied from the fuel tank 27. Further, the hydrophilic conductive layer 13 has a role of controlling the diffusion of water generated at the cathode into the anode catalyst layer 11 and the first fuel diffusion layer 12 and adjusts the balance of water between the anode and the cathode. It has a function.
  • the hydrophilic conductive layer 13 is exposed to high-concentration methanol, the hydrophilic conductive layer 13 is required to be hardly soluble in methanol.
  • the hydrophilic conductive layer 13 is water retentive against moisture.
  • the hydrophilic conductive layer 13 is composed of a coating film containing conductive particles and a hydrophilic polymer.
  • the content of the hydrophilic polymer in the hydrophilic conductive layer can be appropriately determined according to the molecular weight and the like.
  • the molecular weight of the hydrophilic polymer can be controlled by, for example, the degree of polymerization. For example, when polyvinyl alcohol having a degree of polymerization of about 4500 is used as the hydrophilic polymer, a desired effect can be obtained if it is contained at about 1 wt%.
  • the degree of polymerization of the hydrophilic polymer can be determined, for example, by the solution viscosity method.
  • the degree of polymerization of the hydrophilic polymer is about 500 to 10,000. If it is too small, the film-forming ability will be small, and it will be difficult to form hydrophilic conductivity. On the other hand, when the molecular weight is too large, the solubility in a solvent is greatly reduced. In addition to this, there is a risk that the viscosity becomes too large and it becomes difficult to adjust the slurry for the hydrophilic conductive layer.
  • the hydrophilic polymer preferably occupies 1 to 30 wt% of the weight of the hydrophilic conductive layer 13.
  • the hydrophilic polymer is less than 1 wt%, the coating property is deteriorated. On the other hand, if it exceeds 30 wt%, the resistance will increase and the performance will deteriorate. More preferably, the hydrophilic polymer is 5 to 20 wt% of the weight of the hydrophilic conductive layer.
  • hydrophilic polymer any material having a hydrophilic group (polar group) and insoluble in methanol can be used. Specific examples include polyvinyl alcohol (PVA) and methyl cellulose, but are not limited thereto.
  • PVA polyvinyl alcohol
  • methyl cellulose but are not limited thereto.
  • the resistance to water and methanol can be improved by chemical crosslinking using heat treatment or a part of the polar group.
  • the conductive particles include carbon, graphite, carbon nanotube, and carbon nanofiber. Furthermore, conductive nitrides such as TiN, conductive oxides such as WO 2 , conductive sulfides such as W 2 S, and conductive silicides such as WSi 2 can be used as the conductive particles. It is not limited to.
  • the average particle diameter of the conductive particles can be appropriately selected according to the specific surface area, the oil absorption amount, etc., but is desirably about 0.01 to 10 ⁇ m.
  • the average particle diameter can be usually determined by a laser diffraction scattering method.
  • the concentration of the conductive particles in the hydrophilic conductive layer 13 is preferably about 50 to 99 wt%. When there are too few electroconductive particles, sufficient electroconductivity cannot be ensured. On the other hand, when the conductive particles are excessively contained, film formation may be difficult.
  • the thickness of the hydrophilic conductive layer 13 is preferably in the range of 10 to 100 ⁇ m.
  • the thickness of the hydrophilic conductive layer 13 is less than 10 ⁇ m, a sufficient effect cannot be exhibited.
  • it exceeds 100 ⁇ m the diffusion of methanol as a fuel is greatly suppressed, and a sufficient current density cannot be obtained.
  • Metal oxide may be contained in the hydrophilic conductive layer 13. Water retention improves by containing a metal oxide.
  • the metal oxide include, but are not limited to, silicon oxide, titanium oxide, zirconia oxide, and tin oxide.
  • the second fuel diffusion layer 14 laminated on the hydrophilic conductive layer 13 can be formed using any porous material having conductivity. By providing the second fuel diffusion layer 14, the uniformity of fuel diffusion is improved. Specific examples of materials that can be used for the second fuel diffusion layer 14 include, but are not limited to, porous carbon materials such as carbon paper and carbon cloth.
  • the second fuel diffusion layer 14 can have a microporous layer made of CNF, CNT and nanocarbon particles on the side opposite to the hydrophilic conductive layer 13.
  • the thickness of the second fuel diffusion layer 14 can be appropriately determined according to the amount of catalyst, the composition and thickness of the first fuel diffusion layer and the hydrophilic conductive layer, and the like. However, if the thickness is excessively large, the amount of fuel diffusion may be reduced.
  • the cathode diffusion layer 17 laminated on the cathode catalyst layer 16 serves to uniformly supply the oxidant to the cathode catalyst layer 16 and also serves as a current collector for the cathode.
  • the cathode diffusion layer 17 can be formed using any porous material having conductivity. It is also required that a cathode catalyst layer can be formed on the cathode diffusion layer 17 by coating or sputtering.
  • cathode diffusion layer 17 examples include, but are not limited to, porous carbon materials such as carbon paper and carbon cloth. Carbon paper, carbon cloth, and the like may be subjected to water repellent treatment with a fluororesin.
  • the cathode diffusion layer 17 can have a microporous layer made of CNF, CNT, or nanocarbon particles on the cathode catalyst layer 16 side.
  • An anode current collector 19 is laminated on the second fuel diffusion layer 14, and a cathode current collector 20 is laminated on the cathode diffusion layer 17.
  • the anode current collector 19 and the cathode current collector 20 can be composed of a porous layer such as a hole or a mesh made of a conductive metal material such as gold.
  • a rubber O-ring 21 is disposed between the polymer electrolyte membrane 15 and the anode current collector 19, and a rubber O-ring 22 is disposed between the polymer electrolyte membrane 15 and the cathode current collector 20. Is placed. Such an O-ring prevents fuel leakage and oxidant leakage from the membrane electrode assembly 18.
  • a hydrophobic porous film 23 is laminated on the anode current collector 19, and a laminated body including the cathode current collector 20 is sandwiched between frames 24 and 25.
  • the frames 24 and 25 can have a shape corresponding to the outer edge shape of the fuel cell 10, and can be a rectangular frame, for example.
  • the frames 24 and 25 can be formed of, for example, a thermoplastic polyester resin such as polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the anode-side frame 24 is connected via a gas-liquid separation membrane 26 to a liquid fuel tank 27 that functions as a fuel supply unit.
  • the gas-liquid separation membrane 26 functions as a vapor phase fuel permeable membrane that allows only the vaporized component of the liquid fuel to permeate and does not allow the liquid fuel to permeate.
  • An opening (not shown) is provided for deriving a vaporized component of the fuel in the liquid fuel tank 27, and a gas-liquid separation membrane 26 is disposed so as to close the opening.
  • the gas-liquid separation film 26 has an action of separating the vaporized component of the fuel and the liquid fuel and further vaporizing the liquid fuel.
  • the gas-liquid separation membrane 26 can be made of, for example, a material such as silicone rubber.
  • a permeation adjustment membrane (not shown) can be provided on the gas-liquid separation membrane 26 on the liquid fuel tank 27 side.
  • the permeation amount adjusting membrane adjusts the permeation amount of the vaporized component of the fuel in addition to separating the gas and liquid in the same manner as the gas-liquid separation membrane 26.
  • the permeation amount of the vaporized component by the permeation amount adjusting film can be adjusted by changing the aperture ratio of the permeation amount adjusting film.
  • a material such as polyethylene terephthalate is used for the permeation amount adjusting membrane.
  • the liquid fuel stored in the liquid fuel tank 27 is a methanol aqueous solution having a concentration exceeding 50 mol% or pure methanol.
  • the purity of pure methanol is preferably 95% by weight or more and 100% by weight or less.
  • the vaporized component of liquid fuel means vaporized methanol when liquid methanol is used as the liquid fuel, and when the methanol aqueous solution is used as liquid fuel, the vaporized component of methanol and the vaporized component of water Means an air-fuel mixture consisting of
  • the porous membrane 23 has hydrophobicity and prevents water from entering the channel of the channel plate from the second fuel diffusion layer 14 side through the porous membrane 23.
  • the fuel supply from the flow path is expanded by the porous membrane 23 so as to be supplied uniformly to the second fuel diffusion layer 14.
  • the porous film 23 can be formed using, for example, polytetrafluoroethylene (PTFE), a water-repellent treated silicone sheet, or the like.
  • the porous membrane 23 Since it is disposed between the anode current collector 19 and the flow path plate, the porous membrane 23 further has the following effects.
  • the osmotic pressure phenomenon promotes a phenomenon in which water generated in the cathode catalyst layer 16 moves to the anode catalyst layer 11 through the electrolyte membrane 15. Water that has moved can be prevented from entering the anode current collector 19 and the gas-liquid separation membrane 26 side below the anode current collector 19.
  • the moisturizing layer 28 can be made of, for example, a material such as a polyethylene porous film.
  • the maximum pore diameter is preferably about 20 to 50 ⁇ m. If the maximum pore diameter is less than 20 ⁇ m, air permeability may be reduced. On the other hand, when the maximum pore diameter is larger than 50 ⁇ m, moisture evaporation becomes excessive.
  • the fuel cell 10 may be configured without using the moisturizing layer 28. In this case, it is preferable to install the surface layer 29 on the cathode-side frame 25 to adjust the amount of water stored in the cathode catalyst layer 16 and the amount of water transpiration. 10 may be configured.
  • the fuel cell 10 configured as described above operates with the following reaction.
  • the liquid fuel (for example, aqueous methanol solution) in the liquid fuel tank 27 is vaporized, and the vaporized mixture of methanol and water vapor forms the gas-liquid separation membrane 26, the porous membrane 23, and the anode current collector 19. pass. Further, it is diffused in the second fuel diffusion layer 14 and supplied to the anode catalyst layer 11 through the hydrophilic conductive layer 13 and the first fuel diffusion layer 12.
  • the air-fuel mixture supplied to the anode catalyst layer 11 causes an internal reforming reaction of methanol represented by the following reaction formula (1).
  • Protons (H + ) generated by the internal reforming reaction are conducted through the electrolyte membrane 15 and reach the cathode catalyst layer 16.
  • the air taken in from the air inlet 30 of the surface layer 29 diffuses through the moisturizing layer 28, the cathode current collector 20, and the cathode diffusion layer 17 and is supplied to the cathode catalyst layer 16.
  • the air supplied to the cathode catalyst layer 16 reacts with protons as represented by the following reaction formula (2). By this reaction, water is generated and a power generation reaction occurs.
  • the water storage amount of the cathode catalyst layer 16 becomes larger than the water storage amount of the anode catalyst layer 11.
  • the phenomenon that the water generated in the cathode catalyst layer 16 moves to the anode catalyst layer 11 through the electrolyte membrane 15 by the osmotic pressure phenomenon is promoted.
  • the supply of moisture to the anode catalyst layer 11 depends only on the vapor vaporized from the liquid fuel tank 27, the supply of moisture is promoted, and the internal reforming reaction of methanol in the above-described formula (1) is promoted. Can be made. As a result, the output density can be increased and the high output density can be maintained over a long period of time.
  • liquid fuel tank 27 can be downsized.
  • the fuel cell 10 is configured by laminating the porous membrane 23 so that the porous membrane 23 is on the anode catalyst layer 11 side.
  • methanol can be released to the anode catalyst layer 11 side.
  • the influence of the change in the amount of vaporization of methanol in the liquid fuel tank 27 can be mitigated, and methanol having a predetermined concentration can be uniformly supplied to the anode catalyst layer 11.
  • liquid fuel is not limited to these.
  • the present invention can be applied to a liquid fuel direct supply type fuel cell using ethyl alcohol, isopropyl alcohol, butanol, dimethyl ether, or the like, or an aqueous solution thereof.
  • Example 1 First, about 75 g of zirconia balls were weighed and accommodated in a polyethylene pot. To this, 2.0 g of platinum-supporting carbon (TEC10EPTM70 manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) and 2.0 g of water were added. Furthermore, 3.0 g of 1-propanol and 2.5 g of Nafion solution DE2020 (trade name: manufactured by DuPont) were added and mixed by a ball mill to prepare a slurry for the cathode catalyst layer.
  • platinum-supporting carbon TEC10EPTM70 manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.
  • DE2020 sodiumfion solution
  • the obtained slurry was applied to carbon paper (carbon paper GPH-090 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to water repellent treatment. This was dried at room temperature to produce an air electrode.
  • the amount of catalyst Pt is about 2.0 mg / cm 2 .
  • the obtained slurry was applied to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) treated with water repellent treatment by adding 14 wt% PTFE. After drying this at room temperature, it was cut into 12 cm 2 to produce a fuel electrode.
  • the water-repellent treated carbon paper acts as a diffusion layer (first fuel diffusion layer).
  • the amount of catalyst PtRu was about 1.7 mg / cm 2 .
  • the obtained slurry was applied with an applicator to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to water repellent treatment. At this time, the gap of the applicator was 0.6 mm. This was dried at room temperature, and 12 cm 2 was cut to prepare a diffusion layer with a hydrophilic conductive layer (sample 1).
  • the water-repellent treated carbon paper acts as a diffusion layer (second fuel diffusion layer).
  • the hydrophilic conductive layer was composed of a PVA layer containing graphite particles, and the thickness thereof was 45 ⁇ m.
  • electrolyte membrane As the electrolyte membrane, a fixed electrolyte membrane Nafion 112 manufactured by DuPont was prepared. An air electrode was disposed on one side of the electrolyte membrane, and a fuel electrode and a diffusion layer with a hydrophilic conductive layer were disposed on the other side. The diffusion layer with a hydrophilic conductive layer was disposed with the hydrophilic conductive layer in contact with the fuel electrode. This was pressed under the conditions of 120 ° C. and 30 kgf / cm 2 to produce a membrane electrode assembly (MEA). The electrode areas of the air electrode and the fuel electrode were both 12 cm 2 .
  • MEA membrane electrode assembly
  • this MEA was sandwiched between gold foils having a plurality of openings for taking in air and vaporized methanol to form an anode current collector and a cathode current collector.
  • the laminate in which the MEA, the anode current collector, the cathode current collector, and the porous film were laminated was sandwiched between two resin frames.
  • a rubber O-ring was sandwiched between the MEA air electrode side and one frame, and between the MEA fuel electrode side and the other frame, respectively.
  • the frame on the fuel electrode side was fixed to the liquid fuel tank with screws through a gas-liquid separation membrane.
  • a silicone sheet was used as the gas-liquid separation membrane.
  • a moisturizing layer was formed by disposing a porous plate on the air agent side frame.
  • a stainless steel plate (SUS304) with a thickness of 2 mm formed with air inlets (4 mm diameter, 64 holes) for air intake is arranged to form a surface layer, and by screwing Fixed.
  • a direct methanol fuel cell having a configuration as shown in FIG. 1 was produced.
  • the DMFC liquid fuel tank thus obtained was injected with 5 ml of pure methanol as the liquid fuel.
  • the maximum output value was measured from the current value and the voltage value. As a result, the maximum output value was 30.5 mW / cm 2 .
  • Example 2 Graphite particles (TIMREX KS-6 manufactured by Timcal) 4.0 g as conductive particles, 10.0 g of 5% PVA (PVA polymerization degree 2000) aqueous solution as a conductive polymer, 5.5 g of water, and metal oxide 0.5 g of silica (300CF manufactured by Nippon Aerosil Co., Ltd.) was placed in a polyethylene pot.
  • a slurry for a hydrophilic conductive layer was prepared by dispersing for about 30 minutes with a defoaming machine (Nerimataro (trademark): manufactured by Sinky Corporation).
  • the obtained slurry was applied with an applicator to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to water repellent treatment. At this time, the gap of the applicator was 0.5 mm. This was dried at room temperature, and 12 cm 2 was cut to prepare a diffusion layer with a hydrophilic conductive layer (sample 2).
  • the water-repellent carbon paper acts as a diffusion layer (second fuel diffusion layer).
  • the hydrophilic conductive layer was composed of a layer of PVA containing graphite particles and silica, and the thickness thereof was 45 ⁇ m.
  • Example 2 An MEA was constructed in the same manner as in Example 1 except that the thus obtained diffusion layer with a hydrophilic conductive layer was used, and a DMFC was produced. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 24.2 mW / cm 2 .
  • Example 3 A diffusion layer with a hydrophilic conductive layer was produced in the same manner as in Example 2 except that PTFE added to the carbon paper was changed to 25 wt%.
  • An MEA was constructed in the same manner as in Example 1 except that the obtained diffusion layer with a hydrophilic conductive layer was used, and a DMFC was produced. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. The maximum value of output was 24.5 mW / cm 2 .
  • Example 4 A diffusion layer with a hydrophilic conductive layer was produced in the same manner as in Example 2 except that the PTFE added to the carbon paper was changed to 35 wt%.
  • An MEA was constructed in the same manner as in Example 1 except that the obtained diffusion layer with a hydrophilic conductive layer was used, and a DMFC was produced. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. The maximum output value was 25.6 mW / cm 2 .
  • Example 5 Platinum ruthenium-supported carbon (TEC61E54DM manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) 2.0 g, water 3.0 g, and Nafion solution DE2020 (trade name: manufactured by DuPont) 5.0 g are mixed in a ball mill to prepare a slurry for the anode catalyst layer. Prepared.
  • TEC61E54DM manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.
  • DE2020 trade name: manufactured by DuPont
  • the obtained slurry was applied to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) treated with water repellent treatment by adding 14 wt% PTFE. After drying this at room temperature, it was cut into 12 cm 2 to produce a fuel electrode.
  • the amount of catalyst PtRu was about 1.7 mg / cm 2 .
  • An MEA was constructed in the same manner as in Example 1 except that the obtained anode was used, and a DMFC was produced. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. The maximum value of output was 21.1 mW / cm 2 .
  • Example 6 First, about 75 g of zirconia balls were weighed and accommodated in a polyethylene pot. To this, 2.0 g of platinum-supporting carbon (TEC10EPTM70 manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) and 2.0 g of water were added. Furthermore, 3.0 g of 1-propanol and 2.5 g of Nafion solution DE2020 (trade name: manufactured by DuPont) were added and mixed by a ball mill to prepare a slurry for the cathode catalyst layer.
  • TEC10EPTM70 manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.
  • DE2020 sodiumfion solution
  • the obtained slurry was applied to carbon paper (carbon paper GPH-090 manufactured by Toray Industries, Inc.) treated with water repellent treatment by adding 14 wt% PTFE. This was dried at room temperature to produce an air electrode.
  • the amount of catalyst Pt was about 2.0 mg / cm 2 .
  • Graphite particles as conductive particles (TIMREX KS-6 manufactured by Timcal) 4.0 g, 10 g of 5% PVA (PVA polymerization degree 2000) aqueous solution as conductive polymer, and silica as metal oxide (manufactured by Nippon Aerosil Co., Ltd.) (300CF) 0.5 g was placed in a polyethylene pot.
  • a slurry for a hydrophilic conductive layer was prepared by dispersing for about 30 minutes with a defoaming machine (Nerimataro (trademark): manufactured by Sinky Corporation).
  • the obtained slurry was applied with an applicator to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) to which 14 wt% of PTFE was added and subjected to water repellent treatment. At this time, the gap of the applicator was 0.6 mm.
  • carbon paper carbon paper GPH-060 manufactured by Toray Industries, Inc.
  • the gap of the applicator was 0.6 mm.
  • the water-repellent carbon paper acts as a diffusion layer (first fuel diffusion layer).
  • the hydrophilic conductive layer was composed of a PVA layer containing graphite particles, and the thickness was 47 ⁇ m.
  • This slurry was applied to the surface of the carbon paper with a hydrophilic conductive layer opposite to the conductive catalyst layer, dried at room temperature, and then cut into 12 cm 2 to prepare a fuel electrode.
  • the water-repellent treated carbon paper acts as a diffusion layer (first fuel diffusion layer).
  • the amount of catalyst PtRu was about 1.7 mg / cm 2 .
  • electrolyte membrane As the electrolyte membrane, a fixed electrolyte membrane Nafion 112 manufactured by DuPont was prepared. An air electrode was disposed on one side of the electrolyte membrane, and a fuel electrode and a diffusion layer with a hydrophilic conductive layer were disposed on the other side. The diffusion layer with a hydrophilic conductive layer was disposed with the hydrophilic conductive layer in contact with the fuel electrode. This was pressed under the conditions of 120 ° C. and 30 kgf / cm 2 to produce a membrane electrode assembly (MEA). The electrode areas of the air electrode and the fuel electrode were both 12 cm 2 .
  • MEA membrane electrode assembly
  • this MEA was sandwiched between gold foils having a plurality of openings for taking in air and vaporized methanol to form an anode current collector and a cathode current collector.
  • the laminate in which the MEA, the anode current collector, the cathode current collector, and the porous film were laminated was sandwiched between two resin frames.
  • a rubber O-ring was sandwiched between the MEA air electrode side and one frame, and between the MEA fuel electrode side and the other frame, respectively.
  • the frame on the fuel electrode side was fixed to the liquid fuel tank with screws through a gas-liquid separation membrane.
  • a silicone sheet was used as the gas-liquid separation membrane.
  • a moisturizing layer was formed by disposing a porous plate on the air agent side frame.
  • a stainless steel plate (SUS304) with a thickness of 2 mm formed with air inlets (4 mm diameter, 64 holes) for air intake is arranged to form a surface layer, and by screwing Fixed.
  • a direct methanol fuel cell having a configuration as shown in FIG. 1 was produced.
  • the DMFC liquid fuel tank thus obtained was injected with 5 ml of pure methanol as the liquid fuel.
  • the maximum output value was measured from the current value and the voltage value. As a result, the maximum output value was 24.1 mW / cm 2 .
  • Example 7 An MEA was constructed and a DMFC was prepared in the same manner as in Example 6 except that carbon paper without water repellent treatment (carbon paper GPH-060 manufactured by Toray Industries, Inc.) was used as the first fuel diffusion layer. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 23.7 mW / cm 2 .
  • Example 8 An MEA was constructed in the same manner as in Example 2 except that the hydrophilic conductive layer was disposed on the anode current collector side, and a DMFC was produced. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 23.5 mW / cm 2 .
  • Example 9 An MEA was constructed in the same manner as in Example 4 except that a diffusion layer with a hydrophilic conductive layer was disposed on the anode current collector side, and a DMFC was produced. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 23.4 mW / cm 2 .
  • Example 10 An MEA was constructed to prepare a DMFC in the same manner as in Example 5 except that the hydrophilic conductive layer of the diffusion layer with a hydrophilic conductive layer was disposed on the anode current collector side. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output was 20.8 mW / cm 2 .
  • Example 11 An MEA was constructed to prepare a DMFC in the same manner as in Example 1 except that the conductive particles used in the hydrophilic conductive layer were changed to carbon particles (Printex 25 manufactured by Degussa). With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 23.8 mW / cm 2 .
  • Example 12 A MEA was constructed and a DMFC was prepared in the same manner as in Example 2 except that the carbon paper with a hydrophilic conductive layer (Sample 2) was heat-treated at 150 ° C. for 10 minutes. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 23.2 mW / cm 2 .
  • the hydrophilic conductive layer of sample 2 is gradually dissolved in boiling water and peeled off. By performing the heat treatment as described above, dissolution and dropping off were not observed even in boiling water for 1 hour, and water resistance was improved.
  • Example 13 An MEA was constructed in the same manner as in Example 2 except that the metal oxide particles used in the hydrophilic conductive layer were changed to titanium oxide (Super Titania F6 manufactured by Showa Denko KK), and a DMFC was prepared. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 23.9 mW / cm 2 .
  • Example 14 Platinum ruthenium-supported carbon (TEC61E54DM manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) 2.0 g, 5 wt% WO 3 -supported TiO 2 0.4 g, water 3.0 g, 1-methoxy-2-propanol 6.0 g, and Nafion solution DE2020 (trade name) : DuPont) 5.0 g was mixed with a ball mill to prepare a slurry for the anode catalyst layer.
  • TEC61E54DM manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.
  • the obtained slurry was applied with an applicator to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to water repellent treatment. At this time, the gap of the applicator was 0.5 mm. After drying this at room temperature, it was cut into 12 cm 2 to produce a fuel electrode. The amount of catalyst PtRu was about 1.7 mg / cm 2 .
  • Example 5 An MEA was constructed in the same manner as in Example 5 except that this fuel electrode was used, and a DMFC was produced.
  • the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 19.9 mW / cm 2 .
  • Example 15 2.0 g of graphite particles (TIMREX KS-6 manufactured by Timcal) as conductive particles, 10 g of 5% PVA (PVA polymerization degree 2000) aqueous solution as conductive polymer, 10 wt% ammonium metatungstate (Nippon Inorganic Chemical Industries, Ltd.) AMT-72) 1.0 g of an aqueous solution and 0.5 g of silica as a metal oxide (300CF manufactured by Nippon Aerosil Co., Ltd.) were placed in a polyethylene pot.
  • a slurry for a hydrophilic conductive layer was prepared by dispersing for about 30 minutes with a defoaming machine (Nerimataro (trademark): manufactured by Sinky Corporation).
  • the obtained slurry was applied with an applicator to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to water repellent treatment. At this time, the gap of the applicator was 0.6 mm. This was dried at room temperature, and 12 cm 2 was cut to prepare a diffusion layer with a hydrophilic conductive layer (sample 15). Further, it was obtained by heating at 150 ° C. for 10 minutes.
  • the water-repellent treated carbon paper acts as a diffusion layer (second fuel diffusion layer).
  • the hydrophilic conductive layer was composed of a PVA layer containing graphite particles, and the thickness thereof was 42 ⁇ m. This hydrophilic conductive layer was not dissolved or slipped in boiling water.
  • a MEA was constructed and a DMFC was prepared in the same manner as in Example 2 except that the diffusion layer with a hydrophilic conductive layer prepared here was used. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 23.5 mW / cm 2 .
  • Example 16 1.98 g of graphite particles (TIMREX KS-6 manufactured by Timcal) as conductive particles, 1.0 g of 5% PVA (PVA: degree of polymerization 4500, manufactured by Kuraray Co.) as a hydrophilic polymer, and ion-exchanged water 5 0.0 g was placed in a polyethylene pot.
  • the average particle size of the graphite particles is about 6 ⁇ m. This was dispersed for about 30 minutes with a defoaming machine (Nerimataro (trademark): manufactured by Sinky Corporation) to prepare a slurry for a hydrophilic conductive layer.
  • a defoaming machine Neimataro (trademark): manufactured by Sinky Corporation
  • the obtained slurry was applied with an applicator to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to water repellent treatment. At this time, the gap of the applicator was 0.6 mm. This was dried at room temperature and cut to 12 cm 2 to prepare a diffusion layer with a hydrophilic conductive layer.
  • carbon paper carbon paper GPH-060 manufactured by Toray Industries, Inc.
  • An MEA was constructed to prepare a DMFC in the same manner as in Example 1 except that the obtained diffusion layer with a hydrophilic conductive layer was used. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 21.5 mW / cm 2 .
  • Example 17 Graphite particles as conductive particles (TIMREX KS-6 manufactured by Timcal) 2.0 g, 10.0 g of 5% PVA (PVA polymerization degree 2000) aqueous solution as a conductive polymer, and silica as a metal oxide (Nippon Aerosil) 0.5 g of 300CF) was accommodated in a polyethylene pot.
  • a slurry for a hydrophilic conductive layer was prepared by dispersing for about 30 minutes with a defoaming machine (Nerimataro (trademark): manufactured by Sinky Corporation).
  • the obtained slurry was applied with an applicator to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to water repellent treatment. At this time, the gap of the applicator was 0.5 mm. This was dried at room temperature, and 12 cm 2 was cut to prepare a diffusion layer with a hydrophilic conductive layer.
  • carbon paper carbon paper GPH-060 manufactured by Toray Industries, Inc.
  • the water-repellent carbon paper acts as a diffusion layer (second fuel diffusion layer).
  • the hydrophilic conductive layer was composed of a PVA layer containing graphite particles and silica, and its thickness was 41 ⁇ m.
  • Example 2 An MEA was constructed and a DMFC was prepared in the same manner as in Example 2 except that the obtained diffusion layer with a hydrophilic conductive layer was used. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 22.1 mW / cm 2 .
  • Example 18 Graphite particles as conductive particles TIMEX KS-6 manufactured by Timcal, 4.0 g, 15.0 g of 5% PVA (PVA polymerization degree 2000) aqueous solution as a conductive polymer, and silica as a metal oxide (Nippon Aerosil Co., Ltd.) 0.25 g (manufactured 300CF) was placed in a polyethylene pot.
  • a slurry for a hydrophilic conductive layer was prepared by dispersing for about 30 minutes with a defoaming machine (Nerimataro (trademark): manufactured by Sinky Corporation).
  • Example 2 An MEA was constructed and a DMFC was prepared in the same manner as in Example 2 except that a slurry having this composition was used. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output was 20.5 mW / cm 2 .
  • Example 19 Graphite particles as conductive particles 4.0% by Timcal TIMREX KS-6), 5.0 g of 5% PVA (PVA polymerization degree 2000) aqueous solution as conductive polymer, and silica as a metal oxide (Nippon Aerosil Co., Ltd.) 0.75 g (manufactured 300CF) was placed in a polyethylene pot.
  • a slurry for a hydrophilic conductive layer was prepared by dispersing for about 30 minutes with a defoaming machine (Nerimataro (trademark): manufactured by Sinky Corporation).
  • Example 20 An MEA was constructed and a DMFC was prepared in the same manner as in Example 2 except that a slurry having this composition was used. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output value was 21.5 mW / cm 2 (Example 20) Graphite particles as conductive particles TIMEX KS-6 manufactured by Timcal 4.0 g, 10.0 g of 5% PVA (PVA polymerization degree 2000) aqueous solution as conductive polymer, 5.0 g of water, cross-linking material (Matsumoto Trading Co., Ltd.) A polyethylene pot was charged with 0.5 g of an organotics TC-315 aqueous solution) and 0.5 g of silica as a metal oxide (300CF manufactured by Nippon Aerosil Co., Ltd.). A slurry for a hydrophilic conductive layer was prepared by dispersing for about 30 minutes with a defoaming machine (Nerima
  • the obtained slurry was applied with an applicator to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to water repellent treatment. At this time, the gap of the applicator was 0.6 mm. This was dried at room temperature and cut to 12 cm 2 to prepare a diffusion layer with a hydrophilic conductive layer.
  • carbon paper carbon paper GPH-060 manufactured by Toray Industries, Inc.
  • the water-repellent treated carbon paper acts as a diffusion layer (second fuel diffusion layer).
  • the hydrophilic conductive layer was composed of a PVA layer containing graphite particles, and the thickness thereof was 42 ⁇ m. This hydrophilic conductive layer was not dissolved or slipped in boiling water.
  • Example 2 An MEA was constructed and a DMFC was prepared in the same manner as in Example 2 except that the obtained diffusion layer with a hydrophilic conductive layer was used. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output was 22.4 mW / cm 2 .
  • Example 21 The carbon paper with hydrophilic conductivity prepared in Example 2 was immersed in a solution obtained by adding 0.5 g of sulfuric acid to 100 g of 5% aqueous glutaraldehyde solution, and dried by heating to crosslink PVA. By this treatment, dissolution in boiling water was not observed.
  • Example 2 An MEA was constructed and a DMFC was prepared in the same manner as in Example 2 except that the obtained diffusion layer with a crosslinked hydrophilic conductive layer was used. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output was 21.8 mW / cm 2 .
  • Example 22 Graphite particles as conductive particles 4.0% by Timcal TIMREX KS-6), 10.0 g of 5% methylcellulose (methylation degree 47%) aqueous solution as a conductive polymer, crosslinker (Organotics TC manufactured by Matsumoto Trading Co., Ltd.) -315 aqueous solution) and 0.5 g of silica as a metal oxide (300CF manufactured by Nippon Aerosil Co., Ltd.) were placed in a polyethylene pot.
  • a slurry for a hydrophilic conductive layer was prepared by dispersing for about 30 minutes with a defoaming machine (Nerimataro (trademark): manufactured by Sinky Corporation).
  • the obtained slurry was applied with an applicator to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to water repellent treatment. At this time, the gap of the applicator was 0.6 mm. This was dried at 70 ° C., and 12 cm 2 was cut to prepare a diffusion layer with a hydrophilic conductive layer.
  • carbon paper carbon paper GPH-060 manufactured by Toray Industries, Inc.
  • the water-repellent treated carbon paper acts as a diffusion layer (second fuel diffusion layer).
  • the hydrophilic conductive layer was composed of a PVA layer containing graphite particles, and the thickness thereof was 42 ⁇ m. This hydrophilic conductive layer was not dissolved or slipped in boiling water.
  • Example 2 An MEA was constructed and a DMFC was prepared in the same manner as in Example 2 except that the obtained diffusion layer with a hydrophilic conductive layer was used. With respect to the obtained DMFC, the maximum output value was measured under the same conditions as in Example 1. As a result, the maximum output was 22.4 mW / cm 2 .
  • the obtained slurry was applied to a carbon paper (carbon paper GPH-090 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to a water repellent treatment. This was dried at room temperature to produce an air electrode.
  • carbon paper GPH-090 manufactured by Toray Industries, Inc.
  • platinum ruthenium-supported carbon (TEC61E54DM manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) 2.0, water 3.0 g, and Nafion solution DE2020 (trade name: manufactured by DuPont) 15.0 g were mixed with a ball mill to form an anode catalyst layer. A slurry was prepared.
  • the obtained slurry was applied to a carbon paper (carbon paper GPH-120 manufactured by Toray Industries, Inc.) to which 14 wt% PTFE was added and subjected to a water repellent treatment. After drying this at room temperature, it was cut into 12 cm 2 to produce a fuel electrode.
  • the amount of catalyst PtRu was about 1.7 mg / cm 2 .
  • electrolyte membrane As the electrolyte membrane, a fixed electrolyte membrane Nafion 112 manufactured by DuPont was prepared. This electrolyte membrane was sandwiched between an air electrode and a fuel electrode. This was pressed under the conditions of 120 ° C. and 30 kgf / cm 2 to produce a membrane electrode assembly (MEA). The electrode areas of the air electrode and the fuel electrode were both 12 cm 2 .
  • MEA membrane electrode assembly
  • a DMFC was prepared in the same manner as in Example 1 except that the obtained MEA was used, and the maximum output value was evaluated. As a result, the maximum output value was 18.2 mW / cm 2 .
  • Example 2 An MEA was produced in the same manner as in Example 1 except that the diffusion layer with a hydrophilic conductive layer was changed to carbon paper (carbon paper GPH-060 manufactured by Toray Industries, Inc.) treated with water repellent treatment by adding 14 wt% PTFE.
  • a DMFC was prepared in the same manner as in Example 1 except that the obtained MEA was used, and the maximum output value was evaluated. The maximum output value was 17.8 mW / cm 2 .
  • Example 3 An MEA was produced in the same manner as in Example 5 except that the diffusion layer with a hydrophilic conductive layer was changed to carbon paper (Toray Industries, Inc., carbon paper GPH-060) that was water-repellent treated by adding 14 wt% PTFE.
  • a DMFC was prepared in the same manner as in Example 1 except that the obtained MEA was used, and the maximum output value was evaluated. The maximum value of output was 10.7 mW / cm 2 .
  • a long-term deterioration test was performed by the following method.
  • the fuel tank part of the passive DMFC evaluation device was made thin so that the amount of accumulated fuel was reduced as much as possible.
  • the pump was controlled to be on-off at the cathode temperature (about 55 ° C.).
  • intermittent power generation was performed at a constant voltage.
  • One cycle of intermittent operation was performed with an operation time of 4 hours and a downtime of 5 hours, and the deterioration of the output after 500 hours was examined.
  • the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage.
  • Various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiments. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, constituent elements over different embodiments may be appropriately combined.

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Abstract

Dans une pile à combustible à méthanol direct, si un combustible concentré est utilisé pour réduire la taille de la pile à combustible à méthanol direct, un phénomène de crossover est augmenté et il est difficile d'obtenir un rendement élevé. En outre, si une couche catalytique anodique est réduite compte tenu de la quantité d'eau de diffusion générée à partir d'une électrode cathodique, il est difficile d'améliorer la stabilité de la génération électrique. La présente invention concerne une électrode anodique destinée à une pile à combustible à méthanol direct comprenant une couche catalytique anodique (11) ; une première couche de diffusion de combustible (12) située sur la couche catalytique anodique ; et une couche conductrice hydrophile (13) située sur la première couche de diffusion de combustible et composée d'une membrane de revêtement contenant des particules conductrices et des macromolécules hydrophiles.
PCT/JP2009/070494 2008-12-24 2009-12-07 Electrode anodique pour pile à combustible à méthanol direct, et complexe membrane-électrode et pile à combustible l'utilisant WO2010073900A1 (fr)

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JP2013089404A (ja) * 2011-10-17 2013-05-13 Shiseido Co Ltd パッシブ型燃料電池及び液体燃料供給部材
JP2013200972A (ja) * 2012-03-23 2013-10-03 Fujikura Ltd ダイレクトメタノール型燃料電池
FR3072608B1 (fr) 2017-10-20 2021-04-02 Commissariat Energie Atomique Structure multicouche integrant un tapis de nanotubes de carbone comme couche de diffusion dans une pemfc

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JP2004221056A (ja) * 2002-12-27 2004-08-05 Honda Motor Co Ltd 膜−電極構造体の製造方法
JP2004342489A (ja) * 2003-05-16 2004-12-02 Sanyo Electric Co Ltd 燃料電池
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