WO2014196159A1 - 膜電極接合体及びその製造方法、並びに固体高分子形燃料電池 - Google Patents
膜電極接合体及びその製造方法、並びに固体高分子形燃料電池 Download PDFInfo
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- WO2014196159A1 WO2014196159A1 PCT/JP2014/002791 JP2014002791W WO2014196159A1 WO 2014196159 A1 WO2014196159 A1 WO 2014196159A1 JP 2014002791 W JP2014002791 W JP 2014002791W WO 2014196159 A1 WO2014196159 A1 WO 2014196159A1
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- electrode assembly
- nonwoven fabric
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- membrane electrode
- electrolyte
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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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
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
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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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a polymer electrolyte fuel cell (hereinafter referred to as a fuel cell), and more particularly to a membrane electrode assembly provided in the fuel cell and a method for producing the same.
- a fuel cell is a device that simultaneously generates electric power and heat by electrochemically reacting a fuel gas containing hydrogen and an oxidant gas containing oxygen such as air.
- a fuel cell is generally configured by stacking a plurality of cells (single cells) and pressurizing them with a fastening member such as a bolt.
- One cell is configured by sandwiching a membrane electrode assembly between a pair of plate-like conductive separators.
- the membrane electrode assembly has its outer peripheral region held by a frame for improving handling properties.
- the membrane electrode assembly including the frame is referred to as an electrode-membrane-frame assembly.
- the membrane electrode assembly is composed of an electrolyte membrane and a pair of electrode layers formed on both surfaces of the electrolyte membrane.
- One of the pair of electrode layers is an anode electrode, and the other is a cathode electrode.
- Each electrode layer is composed of a catalyst layer formed on the surface of the electrolyte membrane and a gas diffusion layer formed on the catalyst layer.
- the fuel cell having the above-described configuration, when the fuel gas is supplied to the anode electrode, the fuel gas is converted into protons in the catalyst layer, and the protons pass through the electrolyte membrane and reach the catalyst layer of the cathode electrode. In combination with the oxidant gas supplied to the cathode electrode, a power generation reaction occurs.
- the catalyst layer is generally composed of a catalyst, a catalyst carrier, and an electrolyte.
- the catalyst generates protons from the fuel gas and combines the protons with the oxidant gas.
- the catalyst carrier takes out electricity generated by the power generation reaction from the catalyst to an external circuit.
- the electrolyte propagates protons generated from the fuel gas.
- Fuel cell power generation performance is affected by reaction efficiency in the catalyst layer, gas diffusivity in the gas diffusion layer and catalyst layer, electrical resistance loss caused by the power generation reaction, proton conductivity, and the like. For this reason, in order to improve the power generation performance of the fuel cell, the propagation path of the fuel gas and the oxidant gas, the electrical conduction path of electricity taken out by the catalyst, the proton conduction path of protons generated from the fuel gas, etc. are favorable. It is required to be formed.
- Protons need to propagate not only inside the catalyst but also from the catalyst to the electrolyte membrane. For this reason, the proton conduction path needs to be formed so that protons can propagate well even in the vicinity of the interface between the catalyst and the electrolyte membrane.
- FIG. 9 is an explanatory view schematically showing the method for manufacturing a membrane electrode assembly disclosed in Patent Document 1. As shown in FIG.
- an electrolyte membrane 101 and a pair of electrode layers 102 are prepared.
- a siloxane monomer 105a is mixed in the electrolyte membrane 101.
- Each electrode layer 102 includes a catalyst layer 103 and a gas diffusion layer 104.
- a siloxane monomer 105b is mixed in the catalyst layer 103.
- FIG. 10 is an explanatory view schematically showing a schematic configuration of the membrane electrode assembly disclosed in Patent Document 2.
- Patent Document 2 discloses a configuration in which a porous support 203 is provided so as to penetrate through the electrolyte membrane 201 and at least a part of the catalyst layer 202.
- Patent Document 1 still has room for improvement in terms of improving power generation performance.
- a polycondensation reaction occurs only in a portion where the siloxane monomer 105a mixed in the electrolyte membrane 101 and the siloxane monomer 105b mixed in the catalyst layer 103 are in contact with each other.
- Siloxane polymers 106 a and 106 b are formed so as to straddle electrolyte membrane 101.
- the portion where the siloxane monomer 105a and the siloxane monomer 105b do not contact each other does not cause the condensation polymerization reaction, so that the siloxane polymers 106a and 106b serving as the proton conduction paths are not formed.
- An object of the present invention is to solve the above-mentioned problems, and provide a membrane electrode assembly that can further improve power generation performance, a method for producing the same, and a polymer electrolyte fuel cell including the membrane electrode assembly. There is to do.
- the membrane electrode assembly of the present invention comprises: An electrolyte membrane; A pair of catalyst layers facing each other across the electrolyte membrane; A pair of gas diffusion layers facing each other across the electrolyte membrane and the pair of catalyst layers; A membrane electrode assembly comprising: At least one of the pair of catalyst layers includes a nonwoven fabric composed of a fibrous structure having proton conduction performance, A part of the nonwoven fabric is configured to be buried in the electrolyte membrane adjacent to the catalyst layer containing the nonwoven fabric.
- the power generation performance can be further improved.
- FIG. 1 is a schematic configuration diagram showing a schematic configuration of a fuel cell according to an embodiment of the present invention.
- FIG. 2 is a schematic exploded view of a fuel cell stack provided in the fuel cell shown in FIG.
- FIG. 3 is a cross-sectional view schematically showing the structure of the membrane electrode assembly provided in the fuel cell shown in FIG.
- FIG. 4 is a cross-sectional view schematically showing the structure of the proton conducting fiber
- FIG. 5A is an explanatory view schematically showing an example of a method of forming proton conductive fibers in the vicinity of the interface between the electrolyte membrane and the catalyst layer;
- FIG. 5B is an explanatory diagram showing a process following FIG. 5A.
- FIG. 5C is an explanatory diagram showing a process following FIG. 5B.
- FIG. 6A is an explanatory view schematically showing another example of a method for forming proton conductive fibers near the interface between the electrolyte membrane and the catalyst layer;
- FIG. 6B is an explanatory diagram showing a process following FIG. 6A.
- FIG. 6C is an explanatory view showing a process following FIG. 6B.
- FIG. 6D is an explanatory diagram illustrating a process following FIG. 6C.
- FIG. 6E is an explanatory diagram showing a process following FIG. 6D.
- FIG. 7A is an explanatory view schematically showing an example of a method for producing a membrane electrode assembly in which proton conductive fibers are formed in the vicinity of the interface between both surfaces of the electrolyte membrane and the catalyst layer;
- FIG. 7B is an explanatory diagram showing a process following FIG. 7A.
- FIG. 7C is an explanatory diagram showing a process following FIG. 7B.
- FIG. 7D is an explanatory diagram illustrating a process following FIG. 7C.
- FIG. 8 is a schematic configuration diagram showing a modification of the fuel cell according to the embodiment of the present invention.
- FIG. 9 is an explanatory view schematically showing a method for producing a membrane electrode assembly described in Patent Document 1.
- FIG. 10 is a cross-sectional view schematically showing a schematic configuration of the membrane electrode assembly described in Patent Document 2. As shown in FIG.
- an electrolyte membrane comprising: At least one of the pair of catalyst layers includes a nonwoven fabric composed of a fibrous structure having proton conduction performance, A part of the nonwoven fabric provides a membrane / electrode assembly embedded in the electrolyte membrane adjacent to the catalyst layer containing the nonwoven fabric.
- the membrane electrode assembly according to the first aspect wherein the non-woven fabric is buried in the electrolyte membrane at a depth of twice or more the diameter of the structure. To do.
- the region containing the non-woven fabric is in the range of 10% to 90% of the thickness of the catalyst layer from the interface between the electrolyte membrane and the catalyst layer.
- the membrane electrode assembly described in 1. is provided.
- the membrane electrode according to any one of the first to third aspects wherein the structure is composed of a mixture of a perfluorosulfonic acid polymer and a fluorocarbon polymer. Provide a joined body.
- the structure is composed of a plurality of fluorocarbon polymer fibers and one perfluorosulfonic acid polymer enclosing the plurality of fluorocarbon polymer fibers.
- the membrane electrode assembly according to any one of the first to fourth aspects is provided.
- the membrane electrode assembly according to the fourth or fifth aspect wherein the weight of the perfluorosulfonic acid polymer is 0.25 to 4 times the weight of the fluorocarbon polymer. I will provide a.
- a membrane electrode assembly according to one is provided.
- any one of the fourth to seventh aspects wherein the catalyst layer includes a perfluorosulfonic acid polymer that is the same material as the perfluorosulfonic acid polymer contained in the structure.
- a membrane electrode assembly according to one is provided.
- the membrane electrode assembly according to any one of the first to eighth aspects, wherein one or more voids exist inside the structure.
- the nonwoven fabric is included in both of the pair of catalyst layers,
- the membrane electrode assembly according to any one of the first to ninth aspects, wherein the nonwoven fabric is disposed only on the cathode electrode side.
- a polymer electrolyte fuel cell comprising the membrane electrode assembly according to any one of the first to eleventh aspects.
- a method for producing a membrane electrode assembly according to the first aspect, Forming the nonwoven fabric on the surface of an undried electrolyte solution containing the material of the electrolyte membrane; Drying the electrolyte solution to form an electrolyte membrane in which a portion of the nonwoven fabric is embedded; Forming the catalyst layer so as to cover the other part of the nonwoven fabric; The manufacturing method of the membrane electrode assembly including this is provided.
- a fourteenth aspect of the present invention there is provided the method for manufacturing a membrane electrode assembly according to the thirteenth aspect, wherein the nonwoven fabric is formed using an electrospinning method.
- FIG. 1 is a schematic configuration diagram showing a schematic configuration of the fuel cell.
- FIG. 2 is a schematic exploded view of a fuel cell stack (hereinafter referred to as a stack) included in the fuel cell shown in FIG.
- the fuel cell 10 is a polymer electrolyte fuel cell, and is configured to cause electric power, heat, and water by electrochemically reacting a fuel gas containing hydrogen and an oxidant gas containing oxygen such as air. Are generated simultaneously.
- a fuel cell 10 includes a stack 30 having a stacked structure in which a plurality of fuel cell cells (or single cells) each having a pair of anode and cathode electrodes are connected in series, and hydrogen from the fuel gas.
- a fuel processor 31 that extracts hydrogen
- an anode humidifier 32 that improves power generation efficiency by humidifying a fuel gas containing hydrogen extracted by the fuel processor 31, and humidifying oxygen-containing gas (oxidant gas)
- a cathode humidifier 33 for performing the above and pumps 34 and 35 for supplying a fuel gas and an oxygen-containing gas, respectively.
- the fuel processor 31, the anode humidifier 32, and the pump 35 constitute a fuel supply device that supplies fuel gas to each cell of the stack 30.
- the cathode humidifier 33 and the pump 35 constitute an oxidant supply device that supplies an oxidant gas to each cell of the stack 30.
- Such a fuel supply device and an oxidant supply device can adopt various other forms as long as they have a function of supplying fuel and an oxidant.
- the fuel cell 10 includes a pump 36 for circulating and supplying cooling water for efficiently removing heat generated in the stack 30 during power generation, and this cooling water (for example, having conductivity).
- a heat exchanger 37 for exchanging heat removed by a liquid such as tap water, and a hot water storage tank 38 for storing the heat-exchanged tap water.
- the fuel cell 10 includes an operation control device 40 that performs operation control for power generation by associating each of these components with each other, and an electric output unit 41 that extracts electricity generated by the stack 30. It has been.
- the stack 30 provided in the fuel cell 10 includes a plurality of unit cells (unit cell modules) 20 that are basic unit configurations, and a current collecting plate 21, an insulating plate 22, and an end plate 23. And are fastened with a predetermined load from both sides.
- Each current collecting plate 21 is provided with a current extraction terminal portion 21a from which current, that is, electricity is extracted during power generation.
- Each insulating plate 22 may be provided with a gas or cooling water inlet or drain not shown.
- Each end plate 23 holds a plurality of unit cells 20, a current collecting plate 21, and an insulating plate 22 that are fastened with a predetermined load by a pressing means (not shown).
- the single cell 20 includes an electrode-membrane-frame assembly 12 in which a membrane electrode assembly 11 is held by a frame (not shown) so as to be sandwiched between a pair of separators 5a and 5b. It is configured.
- the membrane electrode assembly 11 includes an electrolyte membrane 1 and a pair of electrode layers 2 and 2 formed on both surfaces of the electrolyte membrane 1.
- Each electrode layer 2 includes a catalyst layer 3 formed on both surfaces of the electrolyte membrane 1 and a gas diffusion layer 4 formed on the catalyst layer 3.
- the electrolyte membrane 1 is composed of a proton conductive ion exchange membrane.
- the proton conductive ion exchange membrane it is preferable to use a cation exchange membrane composed of a perfluorocarbon polymer having a sulfonic acid group because of its excellent basic characteristics.
- the catalyst layer 3 has a catalyst, a catalyst carrier, and an electrolyte.
- the catalyst generates protons from the fuel gas and combines the protons with the oxidant gas.
- a platinum alloy containing platinum as a main component can be used.
- the catalyst carrier has conductivity and takes out electricity generated by the power generation reaction from the catalyst to an external circuit.
- a carbon support can be used.
- the electrolyte propagates protons generated from the fuel gas.
- the electrolyte for example, Aquivion (registered trademark) manufactured by Solvay Solexis can be used. Since the catalyst dispersed in the catalyst layer 3 causes the fuel gas and the oxidant gas to react with each other, the catalyst layer 3 has a porous structure.
- the gas diffusion layer 4 is generally made of carbon fiber as its base material.
- a base material for example, a carbon fiber woven fabric can be used.
- the separators 5a and 5b may be formed of a gas-impermeable conductive material, such as a resin-impregnated carbon material cut into a predetermined shape or a mixture of carbon powder and resin material. Is generally used.
- a concave groove is formed in a portion of the separators 5a and 5b that contacts the membrane electrode assembly 11.
- the groove portion of the separator 5a is in contact with the gas diffusion layer 4
- a fuel gas flow path for supplying fuel gas to the electrode surface of the anode electrode and carrying away excess gas is formed.
- an oxidant gas passage for supplying oxidant gas to the electrode surface of the cathode electrode and carrying away excess gas is formed.
- FIG. 3 is a cross-sectional view schematically showing the structure of the membrane electrode assembly 11.
- the membrane electrode assembly 11 has a non-woven fabric 6A composed of a fibrous structure (hereinafter referred to as a proton conducting fiber) 6 having proton conducting performance.
- a part of the nonwoven fabric 6A is buried in the electrolyte membrane 1 adjacent to the catalyst layer 3 containing the nonwoven fabric 6A.
- the other part of the nonwoven fabric 6 ⁇ / b> A exposed from the electrolyte membrane 1 is located inside the catalyst layer 3.
- the space between the fibers of the proton conducting fiber 6 is filled with a catalyst.
- the nonwoven fabric 6A is included in both the pair of catalyst layers 3 and 3.
- the nonwoven fabric 6A included in one of the pair of catalyst layers 3 and 3 and the nonwoven fabric 6A included in the other of the pair of catalyst layers 3 and 3 are disposed apart from each other. That is, the nonwoven fabric 6 ⁇ / b> A is disposed so as not to penetrate the electrolyte membrane 1.
- the thickness of the electrolyte membrane 1 and the catalyst layer 3 is, for example, 30 ⁇ m.
- the region containing the nonwoven fabric 6A in the catalyst layer 3 is, for example, in the range of 50% of the thickness of the catalyst layer 3 from the interface between the electrolyte membrane 1 and the catalyst layer 3 (that is, in the range of 15 ⁇ m from the interface).
- protons generated by the catalyst in the catalyst layer 3 can be propagated to the electrolyte membrane 1 through the proton conducting fibers 6 on the anode electrode side.
- the resistance generated at the interface between the catalyst layer 3 on the anode electrode side and the electrolyte membrane 1 can be reduced, and the power generation performance of the fuel cell can be further improved.
- the protons propagated to the electrolyte membrane 1 can be propagated to the catalyst layer 3 on the cathode electrode side through the proton conducting fibers 6. Thereby, the resistance generated at the interface between the catalyst layer 3 on the cathode electrode side and the electrolyte membrane 1 can be lowered, and the power generation performance of the fuel cell can be further improved.
- the nonwoven fabric 6A composed of the proton conductive fibers 6 formed so as to straddle the electrolyte membrane 1 and the catalyst layer 3 functions as an anchor,
- the catalyst layer 3 can be prevented from peeling off from the electrolyte membrane 1.
- the nonwoven fabric 6A is provided so as not to penetrate the electrolyte membrane 1, it is possible to suppress the occurrence of cross leak due to the nonwoven fabric 6A. , It is possible to suppress a decrease in power generation performance.
- the nonwoven fabric 6A may be provided so as to be included in only one of the pair of catalyst layers 3 and 3.
- the nonwoven fabric 6A is preferably provided on the cathode electrode side.
- the region where the nonwoven fabric 6A is included in the catalyst layer 3 is preferably in the range of 10% to 90% of the thickness of the catalyst layer 3 from the interface between the electrolyte membrane 1 and the catalyst layer 3. If it is smaller than 10%, it cannot contribute to the propagation of protons generated by the catalyst existing in the region away from the electrolyte membrane 1 (on the gas diffusion layer 4 side), and sufficient proton conduction performance can be exhibited. It may not be possible. On the other hand, when the ratio is larger than 90%, the nonwoven fabric 6A is disposed in the vicinity of the gas diffusion layer 4, and the transfer of electrons at the interface between the catalyst layer 3 and the gas diffusion layer 4 is hindered. May grow.
- the diameter (average fiber diameter) of the proton conducting fiber 6 is preferably 1 ⁇ m or less.
- the diameter of the proton conducting fiber 6 By setting the diameter of the proton conducting fiber 6 to 1 ⁇ m or less, it becomes possible to form more proton conducting paths from the catalyst to the electrolyte membrane 1. In addition, the contact area between the proton conducting fiber 6 and the catalyst can be increased, and the power generation performance of the fuel cell can be further improved.
- the diameter is larger than 1 ⁇ m, the fiber spacing of the proton conducting fibers 6 becomes narrow, and the catalyst cannot be sufficiently filled, and the necessary power generation capacity may not be ensured.
- the diameter (average fiber diameter) of the proton conducting fiber 6 is preferably 0.01 ⁇ m or more. When the diameter is smaller than 0.01 ⁇ m, sufficient strength of the proton conducting fiber 6 cannot be obtained, and the catalyst layer 3 may be peeled off from the electrolyte membrane 1.
- the nonwoven fabric 6A is buried in the electrolyte membrane 1 at a depth of twice or more the diameter of the proton conducting fiber 6.
- the proton conducting fiber 6 can be used as an anchor to function more reliably, and the catalyst layer 3 can be prevented from peeling off from the electrolyte membrane 1.
- FIG. 4 is a cross-sectional view schematically showing the structure of the proton conducting fiber 6.
- the proton conducting fiber 6 is configured such that a fluorocarbon polymer 52 and a void 53 exist inside a perfluorosulfonic acid polymer 51.
- the weight ratio of the perfluorosulfonic acid polymer to the fluorocarbon polymer is, for example, 5: 5.
- the proton conducting fiber 6 is composed of a mixture of a perfluorosulfonic acid polymer 51 and a fluorocarbon polymer 52.
- the perfluorosulfonic acid polymer 51 has a good affinity for the electrolyte and can improve the proton conduction performance.
- the fluorocarbon polymer 52 can function as a core material, and can improve mechanical strength. Therefore, by configuring the proton conducting fiber 6 as described above, good proton conducting performance and mechanical strength can be obtained, and long-term durability can be ensured.
- the proton conducting fiber 6 is composed of a plurality of fluorocarbon polymer 52 fibers and a single perfluorosulfonic acid polymer 51 enclosing the plurality of fluorocarbon polymer 52 fibers. Yes. Thereby, since the outer surface of the proton conducting fiber 6 in contact with the catalyst layer 3 becomes the perfluorosulfonic acid polymer 51, it is possible to obtain good proton conducting performance and further improve the power generation performance of the fuel cell. it can.
- the proton conducting performance in the proton conducting fiber 6 can be improved, and the power generation characteristics of the fuel cell can be further improved.
- the electrolyte membrane 1 preferably contains a perfluorosulfonic acid polymer that is the same material as the perfluorosulfonic acid polymer contained in the proton conducting fiber 6. In this case, transfer of protons between the proton conducting fiber 6 and the electrolyte membrane 1 can be facilitated, and the power generation performance of the fuel cell can be further improved.
- the catalyst layer 3 preferably contains a perfluorosulfonic acid polymer that is the same material as the perfluorosulfonic acid polymer contained in the proton conducting fiber 6. In this case, transfer of protons between the proton conducting fiber 6 and the catalyst of the catalyst layer 3 can be facilitated, and the power generation performance of the fuel cell can be further improved.
- the weight of the perfluorosulfonic acid polymer 51 is smaller than the weight of the fluorocarbon polymer 52, the proton conducting performance is lowered. Therefore, the weight of the perfluorosulfonic acid polymer 51 is preferably 0.25 times or more the weight of the fluorocarbon polymer 52.
- the weight of the perfluorosulfonic acid polymer 51 is larger than the weight of the fluorocarbon polymer 52, the proton conduction performance is improved.
- the proton conducting fiber 6 absorbs the generated water generated at the time of power generation of the fuel cell and the moisture contained in the fuel gas or oxidant gas and expands and contracts, and the catalyst layer 3 is easily peeled off from the electrolyte membrane 1.
- the weight of the perfluorosulfonic acid polymer 51 is preferably not more than four times the weight of the fluorocarbon polymer 52.
- the proton conducting fiber 6 is formed by melting the perfluorosulfonic acid polymer 51 and the fluorocarbon polymer 52 in an organic solvent and fiberizing them using an electrospinning method.
- the outer surface of the proton conducting fiber 6 can be formed of the perfluorosulfonic acid polymer 51.
- the proton conductive fiber 6 can be suitably disposed at the interface between the electrolyte membrane 1 and the catalyst layer 3.
- a structure in which one or more voids 53 exist in the perfluorosulfonic acid polymer 51 can be realized.
- PVDF polyvinylidene fluoride polymer
- the material of the fluorocarbon polymer 52 may be a material having high durability with respect to the electrolyte membrane 1 and the catalyst layer 3 when the fuel cell 10 is in the power generation state.
- a material of the fluorocarbon polymer 52 a polyvinyl fluoride polymer (hereinafter referred to as PVF), a copolymer composed of a plurality of monomer units constituting a polymer selected from PVDF and PVF, and a mixture of these polymers are used. Also good.
- the molecular weight of the fluorocarbon polymer 52 is preferably 150,000 to 550,000. When the molecular weight of the fluorocarbon polymer 52 is lower than 150,000, sufficient mechanical strength cannot be obtained. On the other hand, when the molecular weight of the fluorocarbon polymer 52 is higher than 550,000, the solubility is lowered and it is difficult to make the fiber.
- 5A to 5C are explanatory diagrams schematically showing the method.
- a PET base material 62 is disposed on a collector 61 connected to the ground, and an electrolyte solution 1A containing the material of the electrolyte membrane 1 is applied onto the PET base material 62.
- a nonwoven fabric 6A is formed on the surface of the undried electrolyte solution 1A.
- the nonwoven fabric 6A is formed using an electrospinning method.
- the electrolyte solution 1A is dried in a drying furnace (not shown) to form the electrolyte membrane 1 in which a part of the nonwoven fabric 6A is buried.
- the catalyst layer 3 is formed on the surface of the electrolyte membrane 1 so as to cover the other part (exposed part) of the nonwoven fabric 6A.
- a part of the nonwoven fabric 6A can be buried in the electrolyte membrane 1 by forming the nonwoven fabric 6A on the surface of the undried electrolyte solution 1A.
- the nonwoven fabric 6A since the nonwoven fabric 6A is formed using the electrospinning method, the nonwoven fabric 6A can be formed directly on the surface of the electrolyte solution 1A, and productivity can be improved.
- the application of the electrolyte solution 1A onto the PET substrate 62 can be performed using, for example, a slit die (not shown) or a bar coater (not shown).
- a slit die not shown
- a bar coater not shown
- the electrolyte material for example, Aquivion (registered trademark) manufactured by Solvay Solexis can be used.
- the solvent of the electrolyte solution 1A for example, a solvent in which water and isopropyl alcohol are mixed at 5: 5 so that the solid content concentration is 5 wt% can be used.
- isopropyl alcohol other alcohol-based materials may be used. Which alcohol-based material is used may be selected in consideration of the drying time of the electrolyte solution 1A. Moreover, you may adjust the ratio of water and alcohol-type material according to the drying time of 1 A of electrolyte solutions. For example, in order to extend the drying time of the electrolyte solution 1A, the ratio of water may be increased.
- a solvent for the electrolyte solution 1A when it is desired to extend the drying time of the electrolyte solution 1A as compared with the case where a mixed solvent of water and an alcohol-based material is used, a solvent having a boiling point higher than that of water may be used.
- the solvent of the electrolyte solution 1A is only water, the contact angle with the proton conducting fiber 6 is increased, the proton conducting fiber 6 is repelled, and the nonwoven fabric 6A composed of the proton conducting fiber 6 is added to the electrolyte solution 1A. It becomes difficult to be buried.
- the thickness of the application of the electrolyte solution 1A may be adjusted so that the thickness of the electrolyte membrane 1 is about 30 ⁇ m when the solvent of the electrolyte solution 1A is dried to form the electrolyte membrane 1.
- the following operation may be performed.
- a syringe 64 is filled with a mixed solution 63 obtained by melting a perfluorosulfonic acid polymer 51 and a fluorocarbon polymer 52 in an organic solvent. Thereafter, a voltage is applied between the metal nozzle 65 attached to the tip of the syringe 64 and the collector 61. Due to the applied voltage, the mixed solution 63 is charged and discharged toward the undried electrolyte solution 1A.
- the mixed solution 63 electrostatically explodes after it is discharged from the metal nozzle 65 until it reaches the undried electrolyte solution 1A. Thereby, proton conductive fibers 6 having a small diameter (average fiber diameter) are formed on the undried electrolyte membrane solution 1A.
- the metal nozzle 65 is moved relative to the collector 61 so that the proton conducting fiber 6 is formed on almost the entire undried electrolyte solution 1A. Thereby, the nonwoven fabric 6A composed of the proton conducting fibers 6 is formed.
- the mixed solution 63 is obtained by melting the perfluorosulfonic acid polymer 51 and the fluorocarbon polymer 52 in an organic solvent.
- the perfluorosulfonic acid polymer 51 for example, Aquivion (registered trademark) manufactured by Solvay Solexis can be used.
- the organic solvent for example, dimethylacetamide (hereinafter referred to as DMAC) can be used. Any organic solvent may be used as long as the perfluorosulfonic acid polymer 51 and the fluorocarbon polymer 52, which are solutes, melt.
- dimethyl sulfoxide, dimethylformamide, acetone or the like may be used as the organic solvent.
- the solid content concentration of the mixed solution 63 is preferably 10 to 25 wt%.
- the solid content concentration of the mixed solution 63 is smaller than 10 wt%, a sufficient average fiber diameter cannot be obtained, the mechanical strength is lowered, and the electrolyte membrane 1 and the catalyst layer 3 may be separated.
- the electrospinning method may not cause sufficient electrostatic explosion and may not be fiberized.
- the diameter of the discharge hole of the mixed solution 63 of the metal nozzle 65 is preferably 0.18 mm to 0.42 mm.
- the diameter is smaller than 0.18 mm, the discharge amount of the mixed solution 63 is reduced, so that the productivity of the proton conducting fiber 6 is lowered.
- the diameter is larger than 0.42 mm, the discharge amount of the mixed solution 63 becomes too large, and a sufficient electrostatic explosion cannot be caused and there is a possibility that the fiberization cannot be performed.
- an air pulse dispenser (not shown) can be used for discharging the mixed solution 63.
- the liquid feeding pressure of the dispenser is preferably 1 kPa to 20 kPa.
- the discharge amount of the mixed solution 63 is reduced, so that the productivity of the proton conducting fiber 6 is lowered.
- the liquid feeding pressure of the dispenser is higher than 20 kPa, the discharge amount of the mixed solution 63 becomes too large, and a sufficient electrostatic explosion cannot be caused and there is a possibility that the fiberization cannot be performed.
- the voltage applied between the metal nozzle 65 and the collector 61 is preferably 1 kV to 20 kV.
- the voltage is lower than 1 kV, sufficient electrostatic explosion cannot occur, and there is a possibility that fiberization cannot be performed.
- the voltage is lower than 1 kV, the discharge speed of the mixed solution 63 is slow, and the proton conducting fiber 6 cannot be buried in the electrolyte membrane 1 to a sufficient depth.
- the voltage is higher than 20 kV, the discharge speed of the mixed solution 63 becomes too fast, and the mixed solution 63 arrives at the electrolyte solution 1A before the electrostatic explosion occurs. May not be obtained.
- the voltage applied between the metal nozzle 65 and the collector 61 is not limited to a positive voltage, and may be a negative voltage.
- the polarity of the voltage may be appropriately selected according to the material to be fiberized.
- the distance between the metal nozzle 65 and the collector 61 is preferably 90 mm to 250 mm.
- the distance is shorter than 90 mm, the time from when the mixed solution 63 is discharged from the metal nozzle 65 until it reaches the electrolyte solution 1A is shortened. For this reason, there is a possibility that the mixed solution 63 arrives at the electrolyte solution 1A before the electrostatic explosion occurs and the proton conductive fiber 6 having an appropriate fineness cannot be obtained.
- the distance is longer than 250 mm, the mixed solution 63 discharged from the metal nozzle 65 spreads over a wide range due to electrostatic explosion. Thereby, the proton conductive fiber 6 is also formed outside the PET base material 62, the material efficiency is deteriorated, and the productivity of the proton conductive fiber 6 is lowered.
- the degree of electrostatic explosion varies depending on the viscosity and amount of the mixed solution 63.
- the mixed solution 63 reaches the electrolyte solution 1A, when the solvent of the mixed solution 63 is not sufficiently dried and is in a wet state, it is considered that the electrostatic explosion is insufficient. In this case, for example, it is possible to cause a sufficient electrostatic explosion by reducing the discharge amount of the mixed solution 63. If it is not desired to reduce the discharge amount of the mixed solution 63 in order to obtain high productivity, the voltage applied between the metal nozzle 65 and the collector 61 is increased or the distance between the metal nozzle 65 and the collector 61 is increased. By lowering the value, it is possible to cause a sufficient electrostatic explosion.
- a metal nozzle provided with a plurality of nozzle holes may be used as the metal nozzle 65.
- the interval between the plurality of nozzle holes is preferably 10 mm or more.
- the charge of the mixed solution 63 discharged from the first nozzle hole and the mixed solution discharged from the second nozzle hole adjacent to the first nozzle hole The electric charge of 63 may repel each other, and an appropriate electrostatic explosion may not be caused.
- the time for drying the electrolyte solution 1A is, for example, 10 minutes, and the temperature for drying the electrolyte solution 1A is, for example, 80 ° C. What is necessary is just to adjust suitably the time and temperature which dry 1 A of electrolyte solutions in a drying furnace according to electrolyte membrane material, the solvent of electrolyte solution, and a density
- the electrolyte membrane 1 obtained by drying the electrolyte solution 1A is preferably subjected to a thermal annealing treatment. Thereby, electrolyte can be crystallized and durability of electrolyte membrane 1 can be improved.
- the temperature of thermal annealing is low, the electrolyte does not crystallize sufficiently, and the durability of the electrolyte membrane 1 may be reduced.
- the temperature of thermal annealing is 10 degreeC or more higher than the glass transition point temperature of electrolyte material. Further, when the thermal annealing time is short, the electrolyte is not sufficiently crystallized, and the durability of the electrolyte membrane 1 may be reduced.
- the time of thermal annealing is 20 minutes or more and 2 hours or less.
- the catalyst layer 3 can be formed, for example, by spray coating or die coating on the surface of the electrolyte membrane 1 with a solution in which a catalyst, a catalyst carrier, and an electrolyte are dispersed in a solvent such as water or ethanol.
- the method for forming the catalyst layer 3 is not particularly limited as long as the catalyst can be filled in the gaps between the proton conducting fibers 6.
- the method of forming the nonwoven fabric 6A near the interface between the electrolyte membrane 1 and the catalyst layer 3 is not limited to the method shown in FIGS. 5A to 5C, and may be the method shown in FIGS. 6A to 6E. Good.
- a PET base material 62 is disposed on a collector 61 connected to the ground, and a nonwoven fabric 6A is formed on the PET base material 62 by an electrospinning method.
- the nonwoven fabric 6A is peeled from the PET base material 62.
- the surface of the PET base material 62 is subjected to a treatment for improving the releasability.
- the electrolyte solution 1 ⁇ / b> A is applied on the PET substrate 62.
- the nonwoven fabric 6A is disposed on the electrolyte solution 1A. Thereby, a part of the nonwoven fabric 6A is buried in the electrolyte solution 1A.
- the electrolyte solution 1A is dried in a drying furnace (not shown). Thereby, the electrolyte membrane 1 in which a part of the nonwoven fabric 6A is buried is formed.
- the catalyst layer 3 is formed on the electrolyte membrane 1. Thereby, a structure in which the nonwoven fabric 6A is formed in the vicinity of the interface between the electrolyte membrane 1 and the catalyst layer 3 can be obtained.
- 7A to 7D are explanatory views schematically showing the method.
- electrolyte membranes 1a having a nonwoven fabric 6A formed on one surface are prepared.
- the electrolyte membrane 1a can be formed by the same method as described with reference to FIG. 5B or FIG. 6D.
- the other surfaces (surfaces on which the nonwoven fabric 6A is not formed) of the two electrolyte membranes 1a and 1a are brought into contact with each other, and the two electrolyte membranes 1a and 1a are sandwiched by a flat press 70. Thereafter, heat and pressure are applied to the two electrolyte membranes 1 a and 1 a by the flat press 70. As a result, as shown in FIG. 7C, the two electrolyte membranes 1a and 1a are integrated (adhered) to form one electrolyte membrane 1.
- catalyst layers 3 and 3 are formed on both surfaces of the electrolyte membrane 1 so as to cover the nonwoven fabrics 6A and 6A.
- the heating temperature by the flat press 70 is low, the two electrolyte membranes 1a and 1a may not be integrated and may be peeled off. For this reason, it is preferable that the heating temperature by the plane press 70 is 10 ° C. or more higher than the glass transition temperature of the electrolyte material.
- heating and pressurization by the flat press 70 are performed in a reduced pressure environment. Thereby, in the state which air mixed between two electrolyte membrane 1a, 1a, both can be prevented from integrating.
- this invention is not limited to the said embodiment, It can implement in another various aspect.
- the two electrolyte membranes 1a and 1a are integrated to form one electrolyte membrane 1, and then the catalyst layers 3 and 3 are formed on both surfaces of the electrolyte membrane 1.
- the catalyst layer 3 may be formed in advance on one surface of each electrolyte membrane 1a so as to cover the nonwoven fabric 6A, and thereafter, heating and pressurization by the flat press 70 may be performed. In this case, since heat and pressure are also applied to the catalyst layer 3, the adhesive strength between the catalyst layer 3 and the electrolyte membrane 1 can be improved.
- the power generation performance can be further improved, so that the solid-state used particularly in home cogeneration systems, fuel cell vehicles, mobile communication base stations, and the like. Useful for polymer fuel cells.
- Electrolyte membrane 1A Electrolyte solution 2 Electrode layer 3 Catalyst layer 4 Gas diffusion layer 5a, 5b Separator 6 Proton conducting fiber 6A Non-woven fabric 10
- Fuel cell 11
- Membrane electrode assembly 12
- Electrode-membrane-frame assembly 20
- Single cell 21
- Current collector 21a Terminal unit
- Terminal unit 22
- Insulating plate 23
- End plate 30
- Fuel processor 32
- Anode humidifier 33
- Cathode humidifier 34, 35, 36 Pump 37 Heat exchanger 38 Hot water storage tank 40
- Operation control device 41 Electric output unit 51 Perfluorosulfonic acid polymer 52 fluorocarbon polymer 53 void 61 collector 62 PET substrate 63 mixed solution 64 syringe 65 metal nozzle 70 flat press
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Abstract
Description
電解質膜と、
前記電解質膜を挟んで互いに対向する一対の触媒層と、
前記電解質膜及び前記一対の触媒層を挟んで互いに対向する一対のガス拡散層と、
を有する膜電極接合体であって、
前記一対の触媒層の少なくとも一方は、プロトン伝導性能を有する繊維状の構造体で構成される不織布を含み、
前記不織布の一部は、当該不織布を含む触媒層と隣接する前記電解質膜の内部に埋没するように構成されている。
前記電解質膜を挟んで互いに対向する一対の触媒層と、
前記電解質膜及び前記一対の触媒層を挟んで互いに対向する一対のガス拡散層と、
を有する膜電極接合体であって、
前記一対の触媒層の少なくとも一方は、プロトン伝導性能を有する繊維状の構造体で構成される不織布を含み、
前記不織布の一部は、当該不織布を含む触媒層と隣接する前記電解質膜の内部に埋没している、膜電極接合体を提供する。
前記一対の触媒層の一方に含まれる不織布と、前記一対の触媒層の他方に含まれる不織布とは互いに離れて配置されている、第1~9態様のいずれか1つに記載の膜電極接合体を提供する。
前記電解質膜の材料を含む未乾燥の電解質溶液の表面上に前記不織布を形成し、
前記電解質溶液を乾燥して、前記不織布の一部が内部に埋没する電解質膜を形成し、
前記不織布の他部を覆うように前記触媒層を形成する、
ことを含む、膜電極接合体の製造方法を提供する。
本発明の実施形態にかかる燃料電池用スタックを備える燃料電池の概略構成について説明する。図1は、当該燃料電池の概略構成を示す模式構成図である。また、図2は、図1に示す燃料電池が備える燃料電池用スタック(以下、スタックという)の模式分解図である。
次いで、図6Dに示すように、電解質溶液1Aが乾燥する前に、電解質溶液1A上に不織布6Aを配置する。これにより、不織布6Aの一部が電解質溶液1A内に埋没する。
次いで、図6Eに示すように、電解質膜1上に触媒層3を形成する。
これにより、電解質膜1と触媒層3との界面付近に不織布6Aが形成された構造物を得ることができる。
1A 電解質溶液
2 電極層
3 触媒層
4 ガス拡散層
5a,5b セパレータ
6 プロトン伝導繊維
6A 不織布
10 燃料電池
11 膜電極接合体
12 電極-膜-枠接合体
20 単セル
21 集電板
21a 端子部
22 絶縁板
23 端板
30 スタック
31 燃料処理器
32 アノード加湿器
33 カソード加湿器
34,35,36 ポンプ
37 熱交換器
38 貯湯タンク
40 運転制御装置
41 電気出力部
51 パーフルオロスルホン酸系ポリマ
52 フルオロカーボン系ポリマ
53 空隙
61 コレクタ
62 PET基材
63 混合溶液
64 シリンジ
65 金属ノズル
70 平面プレス
Claims (14)
- 電解質膜と、
前記電解質膜を挟んで互いに対向する一対の触媒層と、
前記電解質膜及び前記一対の触媒層を挟んで互いに対向する一対のガス拡散層と、
を有する膜電極接合体であって、
前記一対の触媒層の少なくとも一方は、プロトン伝導性能を有する繊維状の構造体で構成される不織布を含み、
前記不織布の一部は、当該不織布を含む触媒層と隣接する前記電解質膜の内部に埋没している、膜電極接合体。 - 前記不織布は、前記構造体の直径の2倍以上の深さで前記電解質膜の内部に埋没している、請求項1に記載の膜電極接合体。
- 前記不織布が含まれる領域は、前記電解質膜と前記触媒層との界面から触媒層の厚みの10%以上90%以下の範囲にある、請求項1又は2に記載の膜電極接合体。
- 前記構造体は、パーフルオロスルホン酸系ポリマとフルオロカーボン系ポリマとの混合体で構成されている、請求項1~3のいずれか1つに記載の膜電極接合体。
- 前記構造体は、複数のフルオロカーボン系ポリマの繊維と、当該複数のフルオロカーボン系ポリマの繊維を内包する1本のパーフルオロスルホン酸系ポリマとで構成されている、請求項1~4のいずれか1つに記載の膜電極接合体。
- 前記パーフルオロスルホン酸系ポリマの重量は、フルオロカーボン系ポリマの重量の0.25倍以上4倍以下である、請求項4又は5に記載の膜電極接合体。
- 前記電解質膜は、前記構造体に含まれるパーフルオロスルホン酸系ポリマと同種の材料であるパーフルオロスルホン酸系ポリマを含む、請求項4~6のいずれか1つに記載の膜電極接合体。
- 前記触媒層は、前記構造体に含まれるパーフルオロスルホン酸系ポリマと同種の材料であるパーフルオロスルホン酸系ポリマを含む、請求項4~7のいずれか1つに記載の膜電極接合体。
- 前記構造体の内部には、1つ以上の空隙が存在する、請求項1~8のいずれか1つに記載の膜電極接合体。
- 前記不織布は、前記一対の触媒層の両方に含まれ、
前記一対の触媒層の一方に含まれる不織布と、前記一対の触媒層の他方に含まれる不織布とは互いに離れて配置されている、請求項1~9のいずれか1つに記載の膜電極接合体。 - 前記不織布は、カソード電極側にのみ配置されている、請求項1~9のいずれか1つに記載の膜電極接合体。
- 請求項1~11のいずれか1つに記載の膜電極接合体を備える固体高分子形燃料電池。
- 請求項1に記載の膜電極接合体の製造方法であって、
前記電解質膜の材料を含む未乾燥の電解質溶液の表面上に前記不織布を形成し、
前記電解質溶液を乾燥して、前記不織布の一部が内部に埋没する電解質膜を形成し、
前記不織布の他部を覆うように前記触媒層を形成する、
ことを含む、膜電極接合体の製造方法。 - 前記不織布は、エレクトロスピニング法を用いて形成される、請求項13に記載の膜電極接合体の製造方法。
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US20170062854A1 (en) | 2017-03-02 |
EP2887435B1 (en) | 2017-03-01 |
EP2887435A4 (en) | 2016-02-17 |
JPWO2014196159A1 (ja) | 2017-02-23 |
JP5665209B1 (ja) | 2015-02-04 |
US10103400B2 (en) | 2018-10-16 |
US20150228993A1 (en) | 2015-08-13 |
US9531025B2 (en) | 2016-12-27 |
EP2887435A1 (en) | 2015-06-24 |
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