WO2020017623A1 - Électrode et procédé de fabrication d'électrode - Google Patents

Électrode et procédé de fabrication d'électrode Download PDF

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WO2020017623A1
WO2020017623A1 PCT/JP2019/028393 JP2019028393W WO2020017623A1 WO 2020017623 A1 WO2020017623 A1 WO 2020017623A1 JP 2019028393 W JP2019028393 W JP 2019028393W WO 2020017623 A1 WO2020017623 A1 WO 2020017623A1
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powder
electrode
alloy
metal
metal powder
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Japanese (ja)
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正己 奥山
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株式会社グラヴィトン
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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 an electrode used as an anode or a cathode, and to an electrode manufacturing method for manufacturing an electrode used as an anode or a cathode.
  • a fuel cell electrode including a platinum catalyst in which platinum is supported on nitrogen-doped carbon obtained by firing a porous metal complex (PCP / MOF) containing zinc as a low-boiling metal (see Patent Document 1). Since this fuel cell electrode uses a porous metal complex (PCP / MOF) containing zinc, which is a low boiling point metal, as a raw material for production, the catalyst carrier is an NDC having a large specific surface area and containing almost no metal derived from the raw material. And a highly active platinum catalyst can be obtained by supporting a small amount of platinum. Further, since no metal derived from a porous metal complex (PCP / MOF), which is a raw material for production, is contained, firing conditions can be freely set. That is, by changing the organic compound linker of the porous metal complex (PCP / MOF) used as a raw material and adjusting the firing temperature, it is possible to control the nitrogen content and crystallinity in the obtained NDC.
  • PCP / MOF porous metal complex
  • platinum-supported carbons are widely used as electrode catalysts for polymer electrolyte fuel cells.
  • the platinum group element is a noble metal and is a scarce resource with a limited production amount. Therefore, it is required to reduce the amount of the platinum group element used. Further, with the spread of polymer electrolyte fuel cells in the future, development of inexpensive electrodes having a non-platinum catalyst using a metal other than expensive platinum is required.
  • An object of the present invention is to provide an electrode which can be produced at low cost without using a platinum group element and which can exhibit substantially the same catalytic activity (catalysis) as an electrode containing a platinum group element, and an electrode of the electrode. It is to provide a manufacturing method. Another object of the present invention is to enable a fuel cell to generate sufficient electricity, supply sufficient electric energy to a load connected to the fuel cell, and efficiently perform electrolysis in a hydrogen gas generator. An object of the present invention is to provide an electrode which can be performed well and can generate a large amount of hydrogen gas, and a method for manufacturing the electrode.
  • a first premise of the present invention for solving the above problem is an electrode used as an anode or a cathode.
  • the feature of the electrode of the present invention on the first premise is that the electrode is fired after compressing a metal powder mixture obtained by uniformly mixing and dispersing at least three types of transition metal powders selected from various transition metals.
  • An alloy powder is formed from an alloy powder obtained by finely pulverizing the obtained alloy molded product, and a carbon electrode plate having a predetermined area having the alloy powder supported on both surfaces.
  • the work of at least three types of selected transition metals is performed. At least three transition metals are selected from various transition metals so that the composite work function of the function is close to the work function of the platinum group element.
  • an alloy powder-laminated porous structure is formed on both surfaces of a carbon electrode plate by an alloy powder that overlaps in the thickness direction of the carbon electrode plate.
  • the particle size of the transition metal powder is in the range of 10 ⁇ m to 200 ⁇ m
  • the particle size of the alloy powder is in the range of 10 ⁇ m to 200 ⁇ m
  • the thickness of the carbon electrode plate is Dimensions range from 0.03 mm to 0.3 mm.
  • the metal powder mixture is mainly composed of Ni (nickel) powder, and the metal powder mixture has a work function of Ni and at least two types of transitions other than Ni. At least two other transition metal powders other than the Ni powder are selected from various transition metals so that the composite work function with the work function of the metal approximates the work function of the platinum group element. I have.
  • the weight ratio of the Ni (nickel) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and one type excluding the Ni powder is used.
  • the weight ratio of transition metal powder to the total weight of the metal powder mixture is in the range of 20% to 50%, and the metal powder mixture of at least one other transition metal powder excluding Ni powder Is in the range of 3% to 20% by weight relative to the total weight.
  • the metal powder mixture is mainly composed of Fe (iron) powder, and the metal powder mixture has a work function of Fe and at least two types of transitions other than Fe. At least two other transition metal powders other than the Fe powder are selected from various transition metals so that the composite work function with the work function of the metal is close to the work function of the platinum group element. I have.
  • the weight ratio of Fe (iron) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and one type of powder excluding Fe powder is used.
  • the weight ratio of the transition metal powder to the total weight of the metal powder mixture is in the range of 20% to 50%, and the metal powder mixture of at least one other transition metal powder excluding Fe powder Is in the range of 3% to 20% by weight relative to the total weight.
  • the metal powder mixture is mainly composed of Cu (copper) powder, and the metal powder mixture has a work function of Cu and at least two transitions other than Cu. Powders of at least two types of transition metals other than Cu powder are selected from various transition metals so that the composite work function with the work function of the metal approximates the work function of the platinum group element. I have.
  • the weight ratio of Cu (copper) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and one type of material excluding Cu powder is used.
  • the weight ratio of the transition metal powder to the total weight of the metal powder mixture is in the range of 20% to 50%, and the metal powder mixture of at least one other transition metal powder excluding Cu powder Is in the range of 3% to 20% by weight relative to the total weight.
  • the electrode of the present invention in an alloy molded product, at least two types of transition metals among the selected transition metals are melted at the time of firing the metal powder mixture, and the molten transition metal is used as a binder to form the transition metal. Powder is joined.
  • a second premise of the present invention for solving the above-mentioned problem is an electrode manufacturing method for manufacturing an electrode used as an anode or a cathode.
  • the feature of the electrode manufacturing method of the present invention based on the second premise is that the electrode manufacturing method is such that the work function of at least three types of transition metals selected from various transition metals is close to the work function of a platinum group element.
  • a transition metal selection step of selecting at least three types of transition metals from various transition metals, and powders of at least three types of transition metals selected in the transition metal selection step are uniformly mixed and dispersed.
  • the electrode manufacturing method of the present invention in the metal powder mixture forming step, at least three kinds of transition metals selected in the transition metal selecting step are finely pulverized to a particle size of 10 ⁇ m to 200 ⁇ m, and an alloy powder preparing step However, the alloy molded product is finely pulverized to a particle size of 10 ⁇ m to 200 ⁇ m.
  • the metal powder mixture produced in the metal powder mixture forming step is pressurized at a pressure of 500 to 800 MPa to form the metal powder compact. Make things.
  • an alloy molded article forming step includes: pressing a metal powder compact at a temperature at which at least two types of transition metals selected from the transition metals selected in the transition metal selecting step are melted.
  • the powder of the transition metal is bonded using the transition metal that has been fired and melted as a binder.
  • the alloy powder supporting step comprises supporting the alloy powder on both sides of a carbon electrode plate having a thickness of 0.03 mm to 0.3 mm, and An alloy powder-laminated porous structure is formed on both sides of the carbon electrode plate by the overlapping alloy powder.
  • an alloy molded product obtained by compressing a metal powder mixture obtained by uniformly mixing and dispersing at least three types of transition metal powders selected from various transition metals, and then firing the same is used for finely forming an alloy molded product.
  • the work function of at least three selected transition metals is formed from a crushed alloy powder and a carbon electrode plate having a predetermined area having the alloy powder supported on both surfaces.
  • the electrode having the alloy powder has substantially the same work function as the electrode containing the platinum group element, It can exhibit substantially the same catalytic activity (catalysis) as an electrode containing an element, and can be suitably used as an electrode of a fuel cell or a hydrogen gas generator.
  • the electrode is made of at least three kinds of transition metals selected from various transition metals in an alloy molded product, is platinum-free without using expensive platinum group elements, and can be manufactured at a low cost.
  • the electrode Since the electrode exhibits substantially the same catalytic activity (catalysis) as an electrode containing a platinum group element, by using the electrode for the fuel cell, it is possible to generate sufficient electricity in the fuel cell, It is possible to supply sufficient electric energy to the load connected to the battery, and to use the electrodes in a hydrogen gas generator to perform electrolysis efficiently and generate a large amount of hydrogen gas. it can.
  • the specific surface area of the alloy powder can be increased, the catalytic action of the alloy powder can be sufficiently utilized, and the electrode having the alloy powder-laminated porous structure is substantially the same as an electrode containing a platinum group element. It has the same work function, can exhibit substantially the same catalytic activity (catalysis) as an electrode containing a platinum group element, and can be suitably used as an electrode of a fuel cell or a hydrogen gas generator.
  • the electrode on which the alloy powder-laminated porous structure is formed exhibits substantially the same catalytic activity (catalysis) as the electrode containing a platinum group element, the use of the electrode in a fuel cell is sufficient for the fuel cell. Power can be generated and sufficient electric energy can be supplied to the load connected to the fuel cell.Electrolysis can be performed efficiently by using the electrodes in a hydrogen gas generator. And a large amount of hydrogen gas can be generated.
  • the particle size of the transition metal powder is in the range of 10 ⁇ m to 200 ⁇ m
  • the particle size of the alloy powder is in the range of 10 ⁇ m to 200 ⁇ m
  • the thickness of the carbon electrode plate is in the range of 0.03 mm to 0.3 mm.
  • the metal powder mixture is mainly composed of Ni (nickel) powder, and the composite work function of the work function of Ni and the work function of at least two types of transition metals other than Ni is close to the work function of a platinum group element.
  • an electrode in which at least two types of transition metal powders other than Ni powder are selected from various transition metals is selected from a work function of Ni and at least two other types of powders other than Ni.
  • At least two other transition metal powders other than the Ni powder are selected from the various transition metals so that the composite work function with the work function of the transition metal approximates the work function of the platinum group element.
  • the electrode having the alloy powder or the alloy powder-laminated porous structure has substantially the same work function as the electrode containing the platinum group element, and has substantially the same catalytic activity (catalysis) as the electrode containing the platinum group element.
  • Catalysis catalytic activity
  • the electrode is made of an alloy molded product made of Ni powder and at least two types of transition metal powder other than Ni powder selected from various transition metals, and expensive platinum group elements are used. It is platinum-free, and electrodes can be manufactured at low cost.
  • the electrode Since the electrode exhibits substantially the same catalytic activity (catalysis) as the electrode containing a platinum group element, sufficient electricity can be generated in the fuel cell by using the electrode in the fuel cell, and Sufficient electric energy can be supplied to the connected load, and the use of the electrode in the hydrogen gas generator enables efficient electrolysis, thereby generating a large amount of hydrogen gas.
  • the weight ratio of the Ni (nickel) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the total weight of the metal powder mixture of one transition metal powder excluding the Ni powder
  • the weight ratio of the transition metal powder to the total weight of the metal powder mixture of at least one other transition metal powder excluding the Ni powder is 3% to 20%.
  • the electrodes in the range are selected from various transition metals so that the composite work function of the work function of Ni and the work function of at least two other transition metals other than Ni approximates the work function of the platinum group element. At least two other transition metal powders other than the Ni powder are selected, and the weight ratio of the Ni powder and the weight ratio of at least one transition metal powder excluding the Ni powder are selected.
  • the electrode having the alloy powder or the alloy powder laminated porous structure has substantially the same work function as the electrode containing the platinum group element, and the electrode containing the platinum group element It is possible to exhibit substantially the same catalytic activity (catalysis) as that of the above, and by using the electrode in the fuel cell, it is possible to generate sufficient electricity in the fuel cell, and to provide sufficient power to the load connected to the fuel cell.
  • electrolysis can be performed efficiently and a large amount of hydrogen gas can be generated.
  • a metal powder mixture is mainly composed of Fe (iron) powder, and a composite work function of a work function of Fe and a work function of at least two types of transition metals other than Fe is close to a work function of a platinum group element.
  • an electrode in which at least two types of transition metal powders other than Fe powder are selected from various transition metals is selected from a work function of Fe and at least two types of other transition metal powders other than Fe.
  • Powders of at least two other transition metals other than Fe powder are selected from various transition metals so that the composite work function with the work function of the transition metal approximates the work function of the platinum group element.
  • the electrode having the alloy powder or the alloy powder-laminated porous structure has substantially the same work function as the electrode containing the platinum group element, and has substantially the same catalytic activity (catalysis) as the electrode containing the platinum group element.
  • Catalysis catalytic activity
  • the electrode is made of an alloy formed from Fe powder and at least two other transition metal powders other than Fe powder selected from various transition metals, and expensive platinum group elements are used. It is platinum-free, and electrodes can be manufactured at low cost.
  • the electrode Since the electrode exhibits substantially the same catalytic activity (catalysis) as the electrode containing a platinum group element, sufficient electricity can be generated in the fuel cell by using the electrode in the fuel cell, and Sufficient electric energy can be supplied to the connected load, and the use of the electrode in the hydrogen gas generator enables efficient electrolysis, thereby generating a large amount of hydrogen gas.
  • the weight ratio of the Fe (iron) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the total of the metal powder mixture of one transition metal powder excluding the Fe powder
  • the electrodes in the range are selected from various transition metals so that the composite work function of the work function of Fe and the work function of at least two types of transition metals other than Fe approximates the work function of the platinum group element. At least two transition metal powders other than the Fe powder are selected, and the weight ratio of the Fe powder and the weight ratio of the at least one transition metal powder except the Fe powder are selected.
  • the electrode having the alloy powder or the alloy powder-laminated porous structure has substantially the same work function as the electrode containing the platinum group element, and is substantially the same as the electrode containing the platinum group element.
  • the electrode can be used in a hydrogen gas generator, so that electrolysis can be performed efficiently and a large amount of hydrogen gas can be generated.
  • the metal powder mixture is mainly composed of Cu (copper) powder, and the work function of Cu and the work function of at least two types of transition metals other than Cu are close to the work function of a platinum group element.
  • an electrode in which at least two types of transition metal powder other than Cu powder are selected from various transition metals is selected from a work function of Cu and at least two other types of powder except Cu.
  • At least two other transition metal powders other than the Cu powder are selected from various transition metals so that the composite work function with the work function of the transition metal approximates the work function of the platinum group element.
  • the electrode having the alloy powder or the alloy powder-laminated porous structure has substantially the same work function as the electrode containing the platinum group element, and has substantially the same catalytic activity (catalysis) as the electrode containing the platinum group element.
  • Catalysis catalytic activity
  • the electrode is made of an alloy molded article made of Cu powder and at least two types of transition metal powder other than Cu powder selected from various transition metals, and expensive platinum group elements are used. It is platinum-free, and electrodes can be manufactured at low cost.
  • the electrode Since the electrode exhibits substantially the same catalytic activity (catalysis) as the electrode containing a platinum group element, sufficient electricity can be generated in the fuel cell by using the electrode in the fuel cell, and Sufficient electric energy can be supplied to the connected load, and the use of the electrode in the hydrogen gas generator enables efficient electrolysis, thereby generating a large amount of hydrogen gas.
  • the weight ratio of the Cu (copper) powder to the total weight of the metal powder mixture is in the range of 30% to 50%, and the total weight of the metal powder mixture of one transition metal powder excluding the Cu powder
  • the electrodes in the range are selected from various transition metals so that the composite work function of the work function of Cu and the work function of at least two other transition metals other than Cu approximates the work function of the platinum group element. At least two transition metal powders other than the Cu powder are selected, and the weight ratio of the Cu powder and the weight ratio of the at least one transition metal powder excluding the Cu powder are selected.
  • the electrode having the alloy powder or the alloy powder-laminated porous structure has substantially the same work function as the electrode containing the platinum group element, and is substantially the same as the electrode containing the platinum group element.
  • the electrode can be used in a hydrogen gas generator, so that electrolysis can be performed efficiently and a large amount of hydrogen gas can be generated.
  • At least two types of transition metals of the selected transition metals are melted during firing of the metal powder mixture, and the electrode to which the transition metal powders are joined using the molten transition metal as a binder is selected from the transition metals among the transition metals.
  • the electrode to which the transition metal powders are joined using the molten transition metal as a binder is selected from the transition metals among the transition metals.
  • an alloy molded product can be produced, and an alloy powder obtained by pulverizing the alloy molded product can be produced.
  • Electrodes can be made.
  • the electrode having an alloy powder or an alloy powder-laminated porous structure has substantially the same work function as an electrode containing a platinum group element, and has substantially the same catalytic activity (catalysis) as an electrode containing a platinum group element.
  • the electrode in a fuel cell By using the electrode in a fuel cell, it is possible to generate sufficient electricity in the fuel cell, supply sufficient electric energy to a load connected to the fuel cell, and By using for a hydrogen gas generator, electrolysis can be performed efficiently and a large amount of hydrogen gas can be generated.
  • various transition metals are selected so that the composite work function of the work functions of at least three types of transition metals selected from various transition metals approximates the work function of the platinum group element.
  • a transition metal selection step of selecting at least three types of transition metals from the mixture, and a metal powder mixture for uniformly mixing and dispersing at least three types of transition metal powders selected in the transition metal selection step The metal powder mixture produced in the preparation step, the metal powder mixture produced step is pressurized at a predetermined pressure to produce a metal powder compact, An alloy molded product making step of baking the obtained metal powder compact at a predetermined temperature to form an alloy molded product, and pulverizing the alloy molded product made by the alloy molded product making process to form an alloy powder.
  • the electrodes are manufactured by an alloy powder preparation process for producing the alloy powder and an alloy powder support process for supporting the alloy powder produced by the alloy powder preparation process on both surfaces of a carbon electrode plate having a predetermined area.
  • a platinum-free electrode that does not use elements can be manufactured at low cost, and it is possible to use the catalyst function sufficiently and reliably, and it has excellent catalytic activity (catalysis) and has a fuel cell and hydrogen gas generator It is possible to produce an electrode that can be suitably used for
  • the step of preparing a metal powder mixture pulverizes at least three kinds of transition metals selected in the step of selecting transition metal into a particle size of 10 ⁇ m to 200 ⁇ m, and the step of preparing an alloy powder converts the alloy molded product to a particle size of 10 ⁇ m to 200 ⁇ m.
  • An electrode manufacturing method for finely pulverizing is capable of producing an alloy molded product by finely pulverizing a transition metal to a particle size in the above range, and an alloy powder by finely pulverizing the alloy molded product to a particle size in the above range.
  • a platinum-less electrode having an alloy powder-laminated porous structure can be produced, and the catalyst function can be used sufficiently and reliably, and the catalyst has excellent catalytic activity (catalysis), An electrode that can be suitably used for a hydrogen gas generator can be made.
  • the electrode manufacturing method in which the metal powder compact is formed by pressing the metal powder mixture produced by the metal powder mixture forming process at a pressure of 500 MPa to 800 Mpa to produce a metal powder compact. By pressing (compressing) at a pressure within the range, a compressed metal powder can be produced, and the compacted metal powder can be fired to produce an alloy molded product, and the alloy molded product can be finely pulverized.
  • a platinum-free electrode having the alloy powder or the alloy powder-laminated porous structure thus prepared can be produced.
  • the alloy molded article production step is a step of firing the metal powder compact at a temperature at which at least two transition metals selected from the transition metals selected in the transition metal selection step are melted, and using the molten transition metal as a binder.
  • the method of manufacturing an electrode for joining powders can produce an alloy molded product by melting at least two types of transition metals among the transition metals, and can produce an alloy powder obtained by pulverizing the alloy molded product.
  • a platinum-less electrode having an alloy powder or an alloy powder-laminated porous structure can be produced.
  • the alloy powder supporting step the alloy powder is supported on both sides of the carbon electrode plate having a thickness of 0.03 mm to 0.3 mm, and the alloy powder is superposed on both surfaces of the carbon electrode plate by the alloy powder overlapping in the thickness direction of the carbon electrode plate.
  • the electrode manufacturing method for forming a body laminated porous structure can produce a platinum-less electrode having an alloy powder laminated porous structure having an increased specific surface area of the alloy powder, and the thickness dimension of the carbon electrode plate can be reduced. By setting the range, the electric resistance of the electrode can be reduced, and a platinum-less electrode capable of flowing a current smoothly can be manufactured.
  • FIG. 3 is a partially enlarged front view of an electrode.
  • FIG. 3 is an end view taken along line AA of FIG. 2.
  • FIG. 7 is a partially enlarged front view of an electrode shown as another example.
  • FIG. 5 is an end view taken along line BB of FIG. 4.
  • FIG. 3 is an exploded perspective view showing an example of a cell using electrodes.
  • FIG. 4 is a side view of a cell using electrodes. The figure explaining the electric power generation of the fuel cell (polymer electrolyte fuel cell) using an electrode. The figure which shows the result of the electromotive force test of an electrode. The figure which shows the result of the IV characteristic test of an electrode. The figure explaining the electrolysis of the hydrogen gas generator using an electrode.
  • FIG. 4 is a diagram illustrating a method for manufacturing an electrode.
  • FIG. 1 is a perspective view of the electrode 10A shown as an example.
  • 2 is a partially enlarged front view of the electrode 10A
  • FIG. 3 is an end view taken along line AA of FIG.
  • the thickness direction is indicated by an arrow X
  • the radial direction is indicated by an arrow Y.
  • the electrode 10A is used as an anode (anode) or a cathode (cathode), and is used as an electrode (catalyst) of the fuel cell 21 (see FIG. 6) and an electrode (catalyst) of the hydrogen gas generator 30 (see FIG. 11).
  • the electrode 10A has a front surface 11 and a rear surface 12, has a predetermined area and a predetermined thickness, and has a square planar shape.
  • the planar shape of the electrode 10A (including the electrode 10B) is not particularly limited, and may be formed into any other planar shape such as a circle, an ellipse, and a polygon according to the application in addition to a square.
  • the electrode 10A is formed of an alloy powder 13 (alloy powder) and a carbon electrode plate 14 having a predetermined area.
  • the alloy powder 13 is made by finely pulverizing an alloy molded product 42 (alloy molded product) (see FIG. 12).
  • the alloy powder 13 has a particle size in the range of 10 ⁇ m to 200 ⁇ m.
  • the alloy molded product 42 is a metal powder mixture 40 (see FIG. 12) in which at least three types of transition metal powders selected from various transition metals that have been processed into a powder form (finely pulverized) are uniformly mixed and dispersed. It is made by firing (sintering) after compressing. As the transition metal, a 3d transition metal or a 4d transition metal is used.
  • Ti titanium
  • Cr chromium
  • Mn manganese
  • Fe iron
  • Co cobalt
  • Ni nickel
  • Cu copper
  • Zn zinc
  • Nb niobium
  • Mo mobdenum
  • Ag silver
  • Transition metal powders include powdered (pulverized) Ti (titanium) powder, powdered (pulverized) Cr (chromium) powder, and powdered (pulverized) Mn (manganese) powder, powdered (fine pulverized) Fe (iron) powder, powdered (fine pulverized) Co (cobalt) powder, powdered (fine pulverized) ) Powdered (pulverized) Cu (copper) powder, powdered (pulverized) Zn (zinc) powder, powdered (fine) Nb (niobium) powder pulverized, Mo (molybdenum) powder pulverized (finely pulverized), and Ag (silver) powder pulverized are used.
  • Ti powder Ti processed into powder (finely pulverized)
  • Cr powder Cr processed into powder (fine pulverized)
  • Mn powder processed into powder (fine pulverized) Mn
  • Fe powder Fe powdered (pulverized)
  • Co powder Co powdered (pulverized)
  • Ni powder powder ( Ni) finely pulverized
  • Cu powder Cu finely pulverized
  • Zn powder Zn finely pulverized
  • Nb powder powder (powder) Nb
  • Mo powder Mo that has been processed (pulverized) into powder
  • Ag powder Au that has been processed (pulverized) into powder
  • the transition metal is selected so that the composite work function of the work functions (energy required to extract electrons from a substance) of at least three selected transition metals is close to the work function of the platinum group element.
  • At least three types of transition metals are selected.
  • the work function of Ti is 4.14 (eV)
  • the work function of Cr is 4.5 (eV)
  • the work function of Mn is 4.1 (eV)
  • the work function of Fe is 4.67 (eV).
  • the work function of Co is 5.0 (eV)
  • the work function of Ni is 5.22 (eV)
  • the work function of Cu is 5.10 (eV)
  • the work function of Zn is 3.63.
  • the work function of Nb is 4.01 (eV)
  • the work function of Mo is 4.45 (eV)
  • the work function of Ag is 4.31 (eV).
  • the work function of platinum is 5.65 (eV).
  • Ni (nickel) powder processed into a powder form (finely pulverized) is used as a main component, and processed into a powdered form excluding Ni powder and Ni (finely pulverized). At least two other transition metals (powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Fe (iron), powder Co (cobalt), powder Powder (Cu), powder Zn (zinc), powder Nb (niobium), powder Mo (molybdenum), powder Ag (silver) (at least two types).
  • the metal powder mixture 40 is uniformly mixed and dispersed.
  • the metal powder mixture 40 obtained by mixing Ni (nickel) powder as a main component and at least two kinds of transition metal powders other than Ni is made of a Ni work function and at least two other kinds of powder except Ni. At least two types of transition metal powders other than Ni powder are selected from various transition metals so that the work function of the transition metal and the work function of the transition metal are close to the work function of the platinum group element. Have been.
  • the alloy molded product 42 containing Ni powder as a main component at least two kinds of transition metals selected from the selected transition metals are melted when the metal powder mixture 40 is fired, and the transition metal is used as a binder with the molten transition metal as a binder. Metal powder is bonded.
  • the alloy powder 13 mainly composed of Ni has a particle size of 10 ⁇ m or less after finely pulverizing an alloy molded product 42 made by compressing and firing a metal powder mixture 40 mainly composed of Ni powder. It is a finely pulverized product of 200 ⁇ m.
  • the weight ratio of the Ni powder to the total weight of the metal powder mixture 40 is in the range of 30% to 50%, and the Ni powder Powder of one type of transition metal except Ti (titanium) powder, Cr (chromium) powder, Mn (manganese) powder, Fe (iron) powder, Co (cobalt) powder, Cu (copper) Powder, Zn (zinc) powder, Nb (niobium) powder, Mo (molybdenum) powder, and at least one of Ag (silver) powder).
  • transition metal powder Ti (titanium) powder, Cr (chromium) powder, Mn (manganese) powder, Fe (Iron) powder, Co (cobalt) powder, Cu (copper) powder, Zn (zinc) powder, Nb Niobium) powder, Mo (molybdenum) powder, Ag (silver) weight ratio to the total weight of the metal powder mixture 40 of at least another one) of the powder is in the range of 3% to 20%.
  • transition metal powder Ti (titanium) powder, Cr (chromium) powder, Mn (manganese) powder, Fe (Iron) powder, Co (cobalt) powder, Cu (copper) powder, Zn (zinc) powder, Nb Niobium) powder, Mo (molybdenum) powder, Ag (silver) weight ratio to the total weight of the metal powder mixture 40 of at least another one) of the powder is in the range of 3% to 20%.
  • the alloy powder 13 containing Ni (nickel) as a main component Ni powder, Cu powder, and ZN powder are uniformly mixed and dispersed.
  • the obtained metal powder mixture 40 is compressed and fired to form an alloy molded product 42, and the alloy molded product 42 is finely pulverized with a particle size of 10 ⁇ m to 200 ⁇ m.
  • the weight ratio of the Ni powder to the total weight of the metal powder mixture 40 was 48%
  • the weight ratio of the Cu powder to the total weight of the metal powder mixture 40 was 42%
  • the metal powder mixture was The powder weight ratio of Zn to the total weight of 40 is 10%.
  • the melting point of Ni is 1455 ° C.
  • the melting point of Cu is 1084.5 ° C.
  • the melting point of Zn is 419.85 ° C.
  • the alloy powder 13 containing Ni (nickel) as a main component a metal powder mixture 40 in which Ni powder, Mn powder, and Mo powder are uniformly mixed and dispersed is compressed.
  • the alloy molded product 42 is fired later to form a finely pulverized product having a particle size of 10 ⁇ m to 200 ⁇ m.
  • the weight ratio of the Ni powder to the total weight of the metal powder mixture 40 was 48%
  • the weight ratio of Mn to the total weight of the metal powder mixture 40 was 7%
  • the metal powder mixture was The powder weight ratio of Mo to the total weight of 40 is 45%.
  • the melting point of Ni is 1455 ° C.
  • the melting point of Mn is 1246 ° C.
  • the melting point of Mo is 2623 ° C.
  • a powdered (finely pulverized) Fe (iron) powder is used as a main component, and a powdery powder excluding Fe (Fe) is processed (finely pulverized).
  • a powdery powder excluding Fe (Fe) is processed (finely pulverized).
  • transition metals powder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Co (cobalt), powder Ni (nickel) , Powdery Cu (copper), powdery Zn (zinc), powdery Nb (niobium), powdery Mo (molybdenum), powdery Ag (silver) (at least two kinds of powders) Are uniformly mixed and dispersed.
  • the alloy molded product 42 containing Fe powder as a main component at least two transition metals of the selected transition metals are melted at the time of firing the metal powder mixture 40, and the transition metal is used as a binder with the molten transition metal as a binder. Metal powder is bonded.
  • the alloy powder 13 containing Fe as a main component has a particle size of 10 ⁇ m or less after finely pulverizing an alloy molded product 42 made by compressing and firing a metal powder mixture 40 containing Fe powder as a main component. It is a finely pulverized product of 200 ⁇ m.
  • the weight ratio of the Fe powder to the total weight of the metal powder mixture 40 is in the range of 30% to 50%, and the Fe powder Powder (Ti (titanium) powder, Cr (chromium) powder, Mn (manganese) powder, Co (cobalt) powder, Ni (nickel) powder, Cu (copper) except for Powder, Zn (zinc) powder, Nb (niobium) powder, Mo (molybdenum) powder, and at least one of Ag (silver) powder).
  • the Fe powder Powder Ti (titanium) powder, Cr (chromium) powder, Mn (manganese) powder, Co (cobalt) powder, Ni (nickel) powder, Cu (copper) except for Powder, Zn (zinc) powder, Nb (niobium) powder, Mo (molybdenum) powder, and at least one of Ag (silver) powder).
  • Powder of at least one other transition metal except Ti powder (Ti (titanium) powder, Cr (chromium) powder, Mn (manganese) powder, Co (Cobalt) powder, Ni (nickel) powder, Cu (copper) powder, Zn (zinc) powder
  • Ti powder Ti (titanium) powder, Cr (chromium) powder, Mn (manganese) powder, Co (Cobalt) powder, Ni (nickel) powder, Cu (copper) powder, Zn (zinc) powder
  • the weight ratio of Nb (niobium) powder, Mo (molybdenum) powder, or at least one of Ag (silver) powder) to the total weight of the metal powder mixture 40 ranges from 3% to 20%. It is in.
  • the alloy powder 13 containing Fe (iron) as a main component As a specific example of the alloy powder 13 containing Fe (iron) as a main component (alloy powder containing Fe as a main component), Fe powder, Ni powder, and Cu powder are uniformly mixed and dispersed.
  • the obtained metal powder mixture 40 is compressed and fired to form an alloy molded product 42, and the alloy molded product 42 is finely pulverized with a particle size of 10 ⁇ m to 200 ⁇ m.
  • the alloy powder 13 had a Fe powder weight ratio of 48% with respect to the total weight of the metal powder mixture 40, a Ni powder weight ratio of 48% with respect to the total weight of the metal powder mixture 40, and a metal powder mixture of The powder weight ratio of Cu to the total weight of 40 is 4%.
  • the melting point of Fe is 1536 ° C.
  • the melting point of Ni is 1455 ° C.
  • the melting point of Cu is 1084.5 ° C.
  • the Cu powder and the Ni powder are melted, and the molten Cu and Ni serve as a binder to form Fe. Powder is joined.
  • the alloy powder 13 containing Fe (iron) as a main component a metal powder mixture 40 in which Fe powder, Ti powder, and Ag powder are uniformly mixed and dispersed is compressed.
  • the alloy molded product 42 is fired later to form a finely pulverized product having a particle size of 10 ⁇ m to 200 ⁇ m.
  • the weight ratio of Fe powder to the total weight of the metal powder mixture 40 was 48%
  • the weight ratio of Ti to the total weight of the metal powder mixture 40 was 46%
  • the metal powder mixture was 40%.
  • the powder weight ratio of Ag to the total weight of 40 is 6%.
  • the melting point of Fe is 1536 ° C.
  • the melting point of Ti is 1666 ° C.
  • the melting point of Ag is 961.93 ° C.
  • the Ag powder and the Fe powder are melted, and the molten Ag and Fe serve as a binder to form Ti. Powder is joined.
  • Cu (copper) powder processed into fine powder (fine pulverized) is used as a main component, and processed into fine powder excluding Cu powder and Cu (fine pulverized).
  • Other transition metals prowder Ti (titanium), powder Cr (chromium), powder Mn (manganese), powder Fe (iron), powder Co (cobalt), powder Ni (nickel), powdered Zn (zinc), powdered Nb (niobium), powdered Mo (molybdenum), powdered Ag (at least two kinds of powders) and powdered Ag (silver) are uniformly mixed. This is a mixed and dispersed metal powder mixture 40.
  • a metal powder mixture 40 obtained by mixing Cu (copper) powder as a main component and at least two types of transition metal powders other than Cu has a work function of Cu and at least two types other than Cu. At least two other transition metal powders other than the Cu powder are selected from various transition metals so that the work function of the transition metal and the work function of the transition metal are close to the work function of the platinum group element. Have been.
  • the alloy molded product 42 containing Cu powder as a main component at least two kinds of selected transition metals are melted at the time of firing the metal powder mixture 40, and the transition metal is used as a binder with the molten transition metal as a binder. Metal powder is bonded.
  • the alloy powder containing Cu as a main component is obtained by compressing a metal powder mixture 40 containing Cu powder as a main component, followed by baking, and finely pulverizing an alloy molded product 42 having a particle size of 10 ⁇ m to 200 ⁇ m. Is finely pulverized.
  • the weight ratio of the Cu powder to the total weight of the metal powder mixture 40 is in the range of 30% to 50%.
  • Powder Ti (titanium) powder, Cr (chromium) powder, Mn (manganese) powder, Fe (iron) powder, Co (cobalt) powder, Ni (nickel) Powder, Zn (zinc) powder, Nb (niobium) powder, Mo (molybdenum) powder, and at least one of Ag (silver) powder).
  • Powder of at least one other transition metal Ti (titanium) powder, Cr (chromium) powder, Mn (manganese) powder, Fe (Iron) powder, Co (cobalt) powder, Ni (nickel) powder, Zn (zinc) powder
  • Ti titanium
  • Cr chromium
  • Mn manganese
  • Fe iron
  • Co cobalt
  • Ni nickel
  • Zn zinc
  • the weight ratio of the metal powder mixture 40 of Nb (niobium) powder, Mo (molybdenum) powder, and at least one of Ag (silver) powder to the total weight of the metal powder mixture 40 is in the range of 3% to 20%. is there.
  • the alloy powder 13 containing Cu (copper) as a main component As specific examples of the alloy powder 13 containing Cu (copper) as a main component (alloy powder containing Cu as a main component), Cu powder, Fe powder, and Zn powder are uniformly mixed and dispersed.
  • the obtained metal powder mixture 40 is compressed and fired to form an alloy molded product 42, and the alloy molded product 42 is finely pulverized with a particle size of 10 ⁇ m to 200 ⁇ m.
  • the weight ratio of Cu powder to the total weight of the metal powder mixture 40 was 48%
  • the powder weight ratio of Fe to the total weight of the metal powder mixture 40 was 48%
  • the metal powder mixture was The powder weight ratio of Zn to the total weight of 40 is 4%.
  • the melting point of Cu is 1084.5 ° C.
  • the melting point of Fe is 1536 ° C.
  • the melting point of Zn is 419.58 ° C.
  • the Zn powder and the Cu powder are melted, and the molten Zn and Cu serve as binders. To join Fe powder.
  • the alloy powder 13 containing Cu (copper) as a main component a metal powder mixture 40 in which Cu powder, Fe powder, and Ag powder are uniformly mixed and dispersed is compressed.
  • the alloy molded product 42 is fired later to form a finely pulverized product having a particle size of 10 ⁇ m to 200 ⁇ m.
  • the weight ratio of Cu powder to the total weight of the metal powder mixture 40 was 48%
  • the powder weight ratio of Fe to the total weight of the metal powder mixture 40 was 46%
  • the metal powder mixture was The powder weight ratio of Ag to the total weight of 40 is 6%.
  • the melting point of Cu is 1084.5 ° C.
  • the melting point of Fe is 1536 ° C.
  • the melting point of Ag is 961.93 ° C.
  • the Ag powder and the Cu powder are melted, and the fused Ag and Cu serve as a binder. To join Fe powder.
  • the carbon electrode plate 14 has a front surface 15 and a rear surface 16, has a predetermined area and a predetermined thickness dimension L1, and has a square planar shape.
  • the planar shape of the carbon electrode plate 14 is not particularly limited, and may be formed into any other planar shape such as a circle, an ellipse, and a polygon in addition to a square.
  • a carbon graphite (graphite) powder of several ⁇ m to several tens ⁇ m and a conductive binder (conductive binder) are formed by cold isostatic pressing and then graphitized at about 3000 ° C. Use a sheet-like electrode material.
  • the carbon electrode plate 14 As another example of the carbon electrode plate 14, a carbon graphite (graphite) powder of several ⁇ m to several tens ⁇ m and a conductive binder (conductive binder) are extruded from an extrusion die and then graphitized at about 3000 ° C. Use a sheet-like electrode material. As the carbon electrode plate 14, glassy carbon can also be used.
  • the thickness L1 of the carbon electrode plate 14 is in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm.
  • a plurality of alloy powders 13 described above are carried on the entire area of the front face 15 and the entire area of the rear face 16 (all the areas on both sides) of the carbon electrode plate 14.
  • the alloy powder 13 is carried on the entire front surface 15 and the entire rear surface 16 (both surfaces) of the carbon electrode plate 14 by a conductive binder (conductive binder) or plasma spraying.
  • the thickness L1 of the carbon electrode plate 14 is less than 0.03 mm, its strength is reduced, and the carbon electrode plate 14 (the electrode 10A (or the electrode 10B)) is easily broken or damaged when an impact is applied. In some cases, the shape cannot be maintained. If the thickness L1 of the carbon electrode plate 14 exceeds 0.3 mm, the electrical resistance of the carbon electrode plate 14 (electrode 10A (or electrode 10B)) increases, and the carbon electrode plate 14 (electrode 10A (or electrode 10B)) The current does not flow smoothly, and when the electrode 10A (or the electrode 10B) is used for the fuel cell 21, the fuel cell 21 cannot generate sufficient electricity, and the electrode 10A (or the electrode 10B) cannot generate enough electricity for the load connected to the fuel cell 21. Cannot supply electrical energy. Also, when the electrode 10A (or the electrode 10B) is used in the hydrogen gas generator 30, electrolysis cannot be performed efficiently, and the hydrogen gas generator 30 can generate a large amount of hydrogen gas in a short time. Can not.
  • the carbon electrode plate 14 has a thickness L1 in the range of 0.03 mm to 0.3 mm, preferably in the range of 0.05 mm to 0.1 mm, the carbon electrode plate 14 (the electrode 10A (or the electrode 10B)) Has high strength and can maintain its shape, and can prevent the carbon electrode plate 14 from being damaged or damaged when an impact is applied to the carbon electrode plate 14. Further, by setting the thickness L1 within the above range, the electric resistance of the carbon electrode plate 14 (the electrode 10A (or the electrode 10B)) can be reduced, and the carbon electrode plate 14 (the electrode 10A (or the electrode 10B)) can be reduced.
  • the electrode 10A When the current flows smoothly, the electrode 10A can generate sufficient electricity in the fuel cell 21 when the electrode 10A is used in the fuel cell 21, and can supply sufficient electric energy to the load connected to the fuel cell 21. it can. Further, when the electrode 10A is used in the hydrogen gas generator 30, electrolysis can be performed efficiently, and a large amount of hydrogen gas can be generated in the hydrogen gas generator 30 in a short time.
  • FIG. 4 is a partially enlarged front view of an electrode 10B shown as another example, and FIG. 5 is an end view taken along line BB of FIG.
  • the electrode 10B is different from the electrode 10A of FIG. 1 in that the alloy powder laminated porous structure 17 is formed by a plurality of alloy powders 13 overlapping in the thickness direction of the carbon electrode plate 14 so that the front surface 15 and the rear surface 16 (both surfaces) of the carbon electrode plate 14 1), and the other configuration is the same as that of the electrode 10A in FIG. 1. Therefore, the same reference numerals as those in FIG. 1 are used, and the description of the electrode 10A in FIG. Detailed description of the other configuration of 10B is omitted.
  • the electrode 10B is used as an anode (anode) or a cathode (cathode), and is used as an electrode (catalyst) of the fuel cell 21 (see FIG. 6) and an electrode (catalyst) of the hydrogen gas generator 30 (see FIG. 11).
  • the electrode 10B has a front surface 11 and a rear surface 12, has a predetermined area and a predetermined thickness dimension, and has a square planar shape.
  • the electrode 10B is formed of an alloy powder 13 (alloy powder) and a carbon electrode plate 14 having a predetermined area and carrying the alloy powder 13 on both surfaces (front and rear surfaces 15, 16).
  • the entire area of the front surface 15 and the entire area of the rear surface 16 (the entire area on both sides) of the carbon electrode plate 14 are formed by a plurality of alloy powders 13 which are overlapped (laminated) in the thickness direction of the carbon electrode plate 14.
  • a structure 17 is formed.
  • the alloy powder 13 is made by finely pulverizing an alloy molded product 42 (alloy molded product).
  • the alloy compact 42 is fired after compressing a metal powder mixture 40 obtained by uniformly mixing and dispersing at least three types of transition metal powders selected from various transition metals processed (pulverized) into powder. (Sintering).
  • the transition metal or metal powder mixture 40, the alloy molding 42, and the alloy powder 13 are the same as those of the electrode 10A of FIG.
  • the particle size of the transition metal powder, the particle size of the alloy powder 13, and the thickness L1 of the carbon electrode plate 14 are the same as those of the electrode 10A of FIG.
  • a large number of fine channels 18 (passage holes) having different diameters are formed in the alloy powder laminated porous structure 17.
  • the flow passages 18 (passage holes) have a plurality of flow openings 19 opening on the front surface 15 side of the carbon electrode plate 14 and a plurality of flow openings 19 opening on the rear surface 16 side of the carbon electrode plate 14. Then, it penetrates through the alloy powder laminated porous structure 17 toward the front surface 11 of the electrode 10B, and penetrates through the alloy powder laminated porous structure 17 toward the rear surface 12 of the electrode 10B.
  • These flow paths 18 extend while bending irregularly in the thickness direction of the carbon electrode plate 14, and also bend irregularly in the radial direction of the carbon electrode plate 14 from the outer peripheral edge of the carbon electrode plate 14 toward the center. While extending.
  • the flow paths 18 that are bent in the thickness direction adjacent to the carbon electrode plate 14 in the radial direction are partially connected in the radial direction, and one flow path 18 and the other flow path 18 communicate with each other.
  • the flow passages 18 that are bent in the radial direction adjacent to the thickness direction of the carbon electrode plate 14 are partially connected in the thickness direction, and one flow passage 18 and the other flow passage 18 communicate with each other.
  • the opening areas (opening diameters) of the flow paths 18 are not uniform in the thickness direction of the carbon electrode plate 14, but are irregularly changed in the thickness direction, and Are not uniform in the radial direction but irregularly change in the radial direction.
  • the flow paths 18 are irregularly opened in the thickness direction and the radial direction while the opening area (opening diameter) increases or decreases.
  • the opening area (opening diameter) of the flow opening 19 opened on the front surface 11 and the flow opening 19 opened on the rear surface 12 are not uniform, and the areas are different.
  • the opening diameters of the flow passages 18 (passage holes) and the flow openings 19 are in the range of 1 ⁇ m to 100 ⁇ m.
  • the alloy powder-laminated porous structure 17 has a porosity in the range of 15% to 30% and a relative density in the range of 70% to 85%.
  • a porosity of the alloy powder laminated porous structure 17 is less than 15% and the relative density exceeds 85%, a large number of fine channels 18 (passage holes) are formed in the alloy powder laminated porous structure 17. Therefore, the specific surface area of the alloy powder-laminated porous structure 17 cannot be increased.
  • the opening area (opening diameter) of the flow path 18 (passage hole) becomes unnecessarily large, and the alloy powder
  • the strength of the laminated porous structure 17 is reduced and the impact is applied, the alloy powder laminated porous structure 17 may be easily broken or damaged, and the form may not be maintained.
  • the alloy powder-laminated porous structure 17 Since the porosity and the relative density of the alloy powder-laminated porous structure 17 are in the above-described ranges, the alloy powder-laminated porous structure 17 has a large number of fine channels 18 (passage holes) having different opening areas (opening diameters). ), The specific surface area of the alloy powder-laminated porous structure 17 can be increased, and the gas or liquid flows through the flow passages 18 (passage holes) while the gas or liquid flows through the alloy powder-laminated porous structure. The contact surface (the surface of the alloy powder 13) of the structure 17 can be widely contacted.
  • the density of the alloy powder-laminated porous structure 17 is in the range of 5.0 g / cm 2 to 7.0 g / cm 2 .
  • the density of the alloy powder-laminated porous structure 17 is less than 5.0 g / cm 2 , the strength of the alloy powder-laminated porous structure 17 is reduced, and when the impact is applied, the alloy powder-laminated porous structure 17 is reduced. It may be easily broken or damaged, and its form cannot be maintained.
  • the density of the alloy powder-laminated porous structure 17 exceeds 7.0 g / cm 2 , many fine channels 18 (passage holes) are not formed in the alloy powder-laminated porous structure 17, and the alloy powder-laminated porous structure 17 The specific surface area of the porous structure 17 cannot be increased.
  • the alloy powder-laminated porous structure 17 formed on both surfaces (front and rear surfaces 15, 16) of the carbon electrode plate 14 is within the above range, the alloy powder-laminated porous structure 17 is formed by a large number of fine flows. It is formed into a porous structure having passages 18 (passage holes), and the specific surface area of the alloy powder laminated porous structure 17 can be increased. The liquid can be brought into wide contact with the contact surface of the alloy powder-laminated porous structure 17 (the surface of the alloy powder 13).
  • the transition metal powder has a particle size of less than 10 ⁇ m, the transition metal may block the flow path 18 (passage hole) and form a large number of fine flow paths 18 in the alloy powder laminated porous structure 17. Therefore, the specific surface area of the alloy powder-laminated porous structure 17 cannot be increased. If the particle size of the transition metal powder exceeds 200 ⁇ m, the opening area (opening diameter) of the flow path 18 (passage hole) becomes unnecessarily large, and a large number of fine flow The passage 18 cannot be formed, and the specific surface area of the alloy powder laminated porous structure 17 cannot be increased.
  • the alloy powder laminated porous structure 17 is formed into a porous structure having a large number of fine channels 18 (passage holes), and the alloy powder laminated porous structure is formed.
  • the specific surface area of the object 17 can be increased, and the gas or liquid flows through the flow path 18 so that the gas or liquid widely contacts the contact surface (the surface of the alloy powder 13) of the alloy powder laminated porous structure 17. Can be done.
  • FIG. 6 is an exploded perspective view showing an example of the cell 20 using the electrodes 10A and 10B
  • FIG. 7 is a side view of the cell 20 using the electrodes 10A and 10B
  • FIG. 8 is a diagram illustrating power generation of the fuel cell 21 (polymer electrolyte fuel cell) using the electrodes 10A and 10B
  • FIG. 9 is a diagram illustrating the results of an electromotive force test of the electrodes 10A and 10B.
  • FIG. 10 is a diagram showing the results of an IV characteristic test of the electrodes 10A and 10B.
  • a fuel electrode 22 (anode) using the electrode 10A or the electrode 10B, and an air electrode 23 (using the electrode 10A or the electrode 10B).
  • a cathode a solid polymer electrolyte membrane 24 (a fluorinated ion exchange membrane having a sulfonic acid group) interposed between the fuel electrode 22 and the air electrode 23, and a separator 25a (bipolar) located outside the fuel electrode 22 in the thickness direction. Plate) and a separator 25b (bipolar plate) located outside the air electrode 23 in the thickness direction.
  • a supply flow path for a reaction gas (hydrogen, oxygen, or the like) is formed (carved) in the separators 25a and 25b.
  • the fuel electrode 22, the air electrode 23, and the solid polymer electrolyte membrane 24 are overlapped and integrated in the thickness direction to form a membrane / electrode assembly (Membrane Electrode Assembly, MEA).
  • MEA Membrane Electrode Assembly
  • the separators 25a and 25b sandwich the membrane / electrode assembly.
  • the solid polymer electrolyte membrane 24, the fuel electrode 22 (electrode 10A or electrode 10B) and the air electrode 23 (electrode 10A or electrode 10B) are laminated by hot pressing.
  • the solid polymer electrolyte membrane 24 and the alloy powder 13 are closely adhered without gaps, or the solid polymer electrolyte membrane 24 and the alloy powder laminated porous structure 17 are overlapped without gaps, and the solid polymer electrolyte
  • the membrane 24 and the alloy powder-laminated porous structure 17 are in close contact with each other without any gap.
  • the fuel cell 21 polymer electrolyte fuel cell
  • a plurality of cells 20 overlap in one direction, and the cells 20 are connected in series to form a cell stack (fuel cell stack).
  • the solid polymer electrolyte membrane 25 has proton conductivity and does not have electronic conductivity.
  • a gas diffusion layer 26a is formed between the fuel electrode 22 and the separator 25a, and a gas diffusion layer 26b is formed between the air electrode 23 and the separator 25b.
  • a gas seal 27a is provided between the fuel electrode 22 and the separator 25a and above and below the gas diffusion layer 26a.
  • a gas seal 27b is provided between the air electrode 23 and the separator 25b and above and below the gas diffusion layer 26b.
  • Protons generated at the fuel electrode 22 flow through the solid polymer electrolyte membrane 24.
  • the protons transferred from the solid polymer electrolyte membrane 24 and the electrons transferred on the conductive wire 28 react with oxygen in the air, and water is generated by a reaction of 4H + + O 2 + 4e ⁇ 2H 2 O.
  • At least three transition metals are selected from the transition metals so that the work function of the work functions of the at least three transition metals is close to the work function of the platinum group element, and the selected at least three transition metals are selected.
  • An alloy powder 13 made of the same is supported on both surfaces (front and rear surfaces 15, 16) of the carbon electrode plate 14, and the alloy powder 13 and the alloy powder laminated porous structure 17 are supported on the fuel electrode 22 (electrode 10A or electrode 10B).
  • the air electrode 23 (electrode 10A or electrode 10B), the fuel electrode 22 and the air electrode 23 exhibit excellent catalytic activity (catalysis), and hydrogen is efficiently decomposed into protons and electrons.
  • the voltage (V) between the fuel electrode 22 and the air electrode 23 (between the electrodes 10A and 10B) was measured for 15 minutes after hydrogen gas injection.
  • the horizontal axis represents the measurement time (min)
  • the vertical axis represents the voltage between the electrodes (V).
  • FIG. 10 shows the results of an IV characteristic test. As described above, there was obtained a result that was not much different from the voltage drop rate of the polymer electrolyte fuel cell using the electrode (platinum electrode) using (supporting) the platinum group element.
  • the platinum-less fuel electrode 22 and the air electrode 23 which do not use the platinum group element emit electrons to generate hydrogen ions. It has been confirmed that the compound has an excellent catalytic action to promote the reaction to become, and has an oxygen reduction function (catalytic action) substantially similar to that of an electrode using platinum.
  • FIG. 11 is a diagram for explaining the electrolysis of the hydrogen gas generator 30 using the electrodes 10A and 10B.
  • an example of the hydrogen gas generator 30 using the electrodes 10A and 10B includes an anode 31 (anode) using the electrode 10A or the electrode 10B and a cathode 32 (cathode) using the electrode 10A or the electrode 10B.
  • a solid polymer electrolyte membrane 33 (a fluorine-based ion exchange membrane having a sulfonic acid group) interposed between the anode 31 and the cathode 32, an anode power supply member 34 and a cathode power supply member 35, an anode water reservoir 36, It is composed of a water reservoir 37 for the cathode, an anode main electrode 38 and a cathode main electrode 39.
  • the hydrogen gas generator 30 supplies electricity to the anode 31 and the cathode 32 to cause an oxidation reaction at the anode 31 and a reduction reaction at the cathode 32 to chemically decompose water.
  • the anode 31, the cathode 32, and the solid polymer electrolyte membrane 33 are overlapped and integrated in the thickness direction to form a membrane / electrode assembly / (Membrane Electrode Assembly, MEA).
  • the anode power supply member 34 and the cathode power supply member 35 are sandwiched.
  • the solid polymer electrolyte membrane 33, the anode 31 (electrode 10A or electrode 10B) and the cathode 32 (electrode 10A or electrode 10B) are laminated by hot pressing, and the solid polymer electrolyte membrane 33 and the alloy powder 13 are tightly spaced.
  • the solid polymer electrolyte membrane 22 and the alloy powder-laminated porous structure 17 overlap without any gap.
  • the solid polymer electrolyte membrane 33 has proton conductivity and does not have electron conductivity.
  • the anode power supply member 34 is located outside the anode 31 and is in close contact with the anode 31 to supply a positive current to the anode 31.
  • the anode water storage tank 36 is located outside the anode power supply member 34 and is in close contact with the anode power supply member 34.
  • the anode main electrode 38 is located outside the anode water storage tank 36 and supplies a positive current to the anode power supply member 34.
  • the cathode power supply member 35 is located outside the cathode 32 and is in close contact with the cathode 32, and supplies a negative current to the cathode 32.
  • the cathode water tank 37 is located outside the cathode power supply member 35 and is in close contact with the cathode power supply member 35.
  • the cathode main electrode 39 is located outside the cathode water storage tank 37 and supplies a negative current to the cathode power supply member 35.
  • water H 2 O
  • the cathode main electrode 39 is supplied with a-current from the power supply.
  • the + current supplied to the anode main electrode 38 is supplied from the anode power supply member 34 to the anode 31 (anode), and the-current supplied to the cathode main electrode 39 is supplied from the cathode power supply member 35 to the cathode 32 (cathode). Is done.
  • At least three transition metals are selected from the transition metals so that the work function of the work functions of the at least three transition metals is close to the work function of the platinum group element, and the selected at least three transition metals are selected.
  • An alloy powder 13 made of the same is supported on both surfaces (front and rear surfaces 15 and 16) of the carbon electrode plate 14, and the alloy powder 13 and the alloy powder laminated porous structure 17 are supported by the anode 31 (electrode 10A or electrode 10B) or the like. Since the cathode 32 (the electrode 10A or the electrode 10B) is formed, the anode 31 and the cathode 32 exhibit excellent catalytic activity (catalysis), the electrolysis is efficiently performed in the hydrogen gas generator 30, and a large amount of Hydrogen gas is generated.
  • the electrode 10A is obtained by compressing a metal powder mixture 40 in which powders of at least three types of transition metals selected from various transition metals are uniformly mixed and dispersed, and then baking the alloy molded product 42 into finely pulverized alloy.
  • the fuel cell 21 can generate sufficient electricity by using the electrode 10A for the fuel cell 21.
  • the use of the electrode 10A for the hydrogen gas generator 30 enables efficient electrolysis, A large amount of hydrogen gas can be generated in the gas generator 30.
  • 10B can increase the specific surface area of the alloy powder-laminated porous structure 17 (alloy powder 13) by forming the alloy powder-laminated porous structure 17 on both sides of the carbon electrode plate 14; While the catalytic action of the body 13 can be fully utilized, the electrode 10B having the alloy powder-laminated porous structure 17 has substantially the same work function as the electrode containing the platinum group element, and It can exhibit substantially the same catalytic activity (catalytic action), and can be suitably used as the electrode 10B of the fuel cell 21 or the hydrogen gas generator 30.
  • the electrode 10B Since the electrode 10B, on which the alloy powder-laminated porous structure 17 is formed, exhibits substantially the same catalytic activity (catalysis) as the electrode containing a platinum group element, the use of the electrode 10B for the fuel cell 21 By generating sufficient electricity in the fuel cell 21 and supplying sufficient electric energy to the load 29 connected to the fuel cell 21, by using the electrode 10 ⁇ / b> B for the hydrogen gas generator 30. In addition, the electrolysis can be performed efficiently, and the hydrogen gas generator 30 can generate a large amount of hydrogen gas.
  • the electrode 10A and the electrode 10B are made of platinum in which the alloy powder 13 and the alloy powder laminated porous structure 17 are formed from at least three types of transition metals selected from various transition metals, and expensive platinum group elements are not used. And the electrodes 10A and 10B can be manufactured at low cost.
  • the electrode 10A or the electrode 10B in which the metal powder mixture 40 (the alloy powder 13 or the alloy powder laminated porous structure 17) is mainly composed of Ni (nickel) powder has the work function of Ni and other elements except for Ni. At least two transition metal powders excluding Ni powder from various transition metals so that the composite work function of at least two transition metals and the work function of the transition metal approximates the work function of the platinum group element.
  • the electrodes 10A and 10B having the alloy powder 13 or the alloy powder laminated porous structure 17 have substantially the same work function as the electrode containing the platinum group element, and Approximately the same catalytic activity (catalytic action) can be exhibited, and it can be suitably used as the electrodes 10A and 10B of the fuel cell 21 and the hydrogen gas generator 30.
  • the electrode 10A or the electrode 10B whose metal powder mixture 40 (the alloy powder 13 or the alloy powder laminated porous structure 17) is mainly composed of Ni (nickel) powder is substantially the same as the electrode containing the platinum group element. Since the electrode 10A and the electrode 10B are used for the fuel cell 21, sufficient electricity can be generated in the fuel cell 21 by using the electrode 10 ⁇ / b> A and the electrode 10 ⁇ / b> B. While sufficient electric energy can be supplied, by using the electrodes 10A and 10B for the hydrogen gas generator 30, the electrolysis can be performed efficiently, and a large amount of hydrogen gas can be supplied to the hydrogen gas generator 30. Can be generated.
  • the electrode 10A or the electrode 10B is made of the alloy powder 13 or the alloy powder-laminated porous structure 17 in which at least two types of transition metal powder other than Ni powder and Ni powder selected from various transition metals are used.
  • the electrodes 10A and 10B can be manufactured at low cost because they are made of a body and are platinum-free without using expensive platinum group elements.
  • the electrode 10A or the electrode 10B in which the metal powder mixture 40 (the alloy powder 13 or the alloy powder laminated porous structure 17) is mainly composed of the powder of Fe (iron) has a work function of Fe and other than Fe. Powders of at least two other transition metals excluding Fe powder from various transition metals so that the composite work function with the work function of at least two transition metals approximates the work function of the platinum group element.
  • the electrodes 10A and 10B having the alloy powder 13 or the alloy powder laminated porous structure 17 have substantially the same work function as the electrode containing the platinum group element, and Approximately the same catalytic activity (catalytic action) can be exhibited, and it can be suitably used as the electrodes 10A and 10B of the fuel cell 21 and the hydrogen gas generator 30.
  • the electrode 10A or the electrode 10B whose metal powder mixture 40 (the alloy powder 13 or the alloy powder laminated porous structure 17) is mainly composed of Fe (iron) powder is substantially the same as the electrode containing the platinum group element. Since the electrode 10A and the electrode 10B are used for the fuel cell 21, sufficient electricity can be generated in the fuel cell 21 by using the electrode 10 ⁇ / b> A and the electrode 10 ⁇ / b> B. While sufficient electric energy can be supplied, by using the electrodes 10A and 10B for the hydrogen gas generator 30, the electrolysis can be performed efficiently, and a large amount of hydrogen gas can be supplied to the hydrogen gas generator 30. Can be generated.
  • the electrode 10A and the electrode 10B are made of the alloy powder 13 or the alloy powder-laminated porous structure 17 in which at least two types of transition metal powder other than Fe powder and Fe powder selected from various transition metals are used. It is made of a body and is platinum-free without using expensive platinum group elements, and the electrodes 10A and 10B can be manufactured at low cost.
  • the electrode 10A or the electrode 10B in which the metal powder mixture 40 (the alloy powder 13 or the alloy powder-laminated porous structure 17) is mainly composed of Cu (copper) powder has a work function of Cu and other than Cu. Powders of at least two other transition metals, excluding Cu powder, from various transition metals so that the composite work function with the work function of at least two types of transition metals approximates the work function of the platinum group element.
  • the electrodes 10A and 10B having the alloy powder 13 or the alloy powder laminated porous structure 17 have substantially the same work function as the electrode containing the platinum group element, and Approximately the same catalytic activity (catalytic action) can be exhibited, and it can be suitably used as the electrodes 10A and 10B of the fuel cell 21 and the hydrogen gas generator 30.
  • the electrode 10A or the electrode 10B whose metal powder mixture 40 (the alloy powder 13 or the alloy powder laminated porous structure 17) is mainly composed of Cu (copper) powder is substantially the same as the electrode containing the platinum group element. Since the catalyst 10 exhibits catalytic activity (catalysis), by using the electrodes 10A and 10B for the fuel cell 21, sufficient electricity can be generated in the fuel cell 21 and sufficient for the load connected to the fuel cell 21. And the electrode 10A and the electrode 10B can be used in the hydrogen gas generator 30 to efficiently perform electrolysis, and generate a large amount of hydrogen gas in the hydrogen gas generator 30. Can be done.
  • the electrode 10A and the electrode 10B are made of the alloy powder 13 or the alloy powder-laminated porous structure 17 having at least two types of transition metal powders other than Cu powder and Cu powder selected from various transition metals. It is made of a body and is platinum-free without using expensive platinum group elements, and the electrodes 10A and 10B can be manufactured at low cost.
  • FIG. 12 is a diagram illustrating a method of manufacturing the electrodes 10A and 10B.
  • the electrode 10A and the electrode 10B are provided with a transition metal selection step S1, a metal powder mixture creation step S2, a metal powder compact creation step S3, an alloy molded article creation step S4, and an alloy powder creation step S5. And an alloy powder supporting step S6.
  • transition metal selection step S1 at least three transition metals are selected from various transition metals so that the composite work function of the work functions of at least three types of transition metals 41 approximates the work function of the platinum group element.
  • Three types of transition metals 41 Ti (titanium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Nb (niobium) ), Mo (molybdenum), Ag (silver)).
  • the transition metal selection step S1 in the metal powder mixture 40 (alloy powder 13 or alloy powder laminated porous structure 17) containing Ni (nickel) as a main component, Cu (copper) and ZN (Zinc) or Mn (Manganese) and Mo (Molybdenum).
  • the metal powder mixture 40 (alloy powder 13 or alloy powder laminated porous structure 17) mainly containing Fe (iron), Ni (nickel) and Cu (copper) are selected, or Ti (titanium) is used. And Ag (silver).
  • metal powder mixture 40 alloy powder 13 or alloy powder laminated porous structure 17 containing Cu (copper) as a main component
  • Fe (iron) and Zn (zinc) are selected, or Fe (iron) is used.
  • Ag silver
  • a metal powder mixture 40 in which powders 42 of at least three types of transition metals 41 selected in the transition metal selection step S1 are uniformly mixed and dispersed is prepared.
  • the metal powder mixture forming step in the metal powder mixture 40 (alloy powder 13 or alloy powder laminated porous structure 17) containing Ni (nickel) as a main component, Ni, Ni selected in the transition metal selection step S1;
  • Each of Cu (copper) and ZN (zinc) is finely pulverized by a fine pulverizer to a particle size of 10 ⁇ m to 200 ⁇ m to prepare a Ni powder 42, a Cu powder 42, and a Zn powder 42.
  • the Ni powder 42, the Cu powder 42, and the Zn powder 42 are put into a mixer, and the Ni powder 42, the Cu powder 42, and the Zn powder 42 are stirred by the mixer.
  • a Ni powder 42, a Cu powder 42, and a Zn powder 42 are uniformly mixed and dispersed to form a metal powder mixture 40.
  • each of Ni (nickel), Mn (manganese), and Mo (molybdenum) selected in the transition metal selection step S1 is finely pulverized to a particle size of 10 ⁇ m to 200 ⁇ m by a fine pulverizer, and the Ni powder 42, Mn Powder 42 and Mo powder 42 are prepared.
  • the Ni powder 42, the Mn powder 42, and the Mo powder 42 are charged into a mixer, and the Ni powder 42, the Mn powder 42, and the Mo powder 42 are stirred by the mixer.
  • the metal powder mixture 40 in which the Ni powder 42, the Mn powder 42, and the Mo powder 42 are mixed and dispersed uniformly is prepared.
  • the Fe selected in the transition metal selection step S1 is selected.
  • Ni (nickel), and Cu (copper) are finely pulverized by a pulverizer to a particle size of 10 ⁇ m to 200 ⁇ m to prepare Fe powder 42, Ni powder 42, and Cu powder 42.
  • the Fe powder 42, the Ni powder 42, and the Cu powder 42 are put into a mixer, and the Fe powder 42, the Ni powder 42, and the Cu powder 42 are stirred by the mixer.
  • the metal powder mixture 30 in which the Fe powder 42, the Ni powder 42, and the Cu powder 42 are mixed and dispersed uniformly is prepared.
  • each of Fe (iron), Ti (titanium), and Ag (silver) selected in the transition metal selection step S1 is finely pulverized to a particle size of 10 ⁇ m to 200 ⁇ m by a fine pulverizer, and the Fe powder 42, Ti And the Ag powder 42 are prepared.
  • the Fe powder 42, the Ti powder 42, and the Ag powder 42 are put into a mixer, and the Fe powder 42, the Ti powder 42, and the Ag powder 42 are stirred by the mixer.
  • the metal powder mixture 40 in which the Fe powder 42, the Ti powder 42, and the Ag powder 42 are mixed and dispersed uniformly is prepared.
  • the Cu selected in the transition metal selection step S1 is selected.
  • Fe (iron) and Zn (zinc) are finely pulverized by a pulverizer to a particle size of 10 ⁇ m to 200 ⁇ m to prepare a Cu powder 42, an Fe powder 42, and a Zn powder 42.
  • the Cu powder 42, the Fe powder 42, and the Zn powder 42 are charged into a mixer, and the Cu powder 42, the Fe powder 42, and the Zn powder 42 are stirred by the mixer.
  • the mixture is mixed to form a metal powder mixture 40 in which the Cu powder 42, the Fe powder 42, and the Zn powder 42 are uniformly mixed and dispersed.
  • each of Cu (copper), Fe (iron), and Ag (silver) selected in the transition metal selection step S1 is finely pulverized to a particle size of 10 ⁇ m to 200 ⁇ m by a fine pulverizer, and the Cu powder 42, Fe And the Ag powder 42 are prepared.
  • the Cu powder 42, the Fe powder 42, and the Ag powder 42 are put into a mixer, and the Cu powder 42, the Fe powder 42, and the Ag powder 42 are stirred by the mixer.
  • the mixture is mixed to form a metal powder mixture 40 in which the Cu powder 42, the Fe powder 42, and the Ag powder 42 are uniformly mixed and dispersed.
  • the metal powder mixture 40 produced in the metal powder mixture production step S2 is pressurized at a predetermined pressure to compress the metal powder mixture 40 into a metal powder having a predetermined area and a predetermined thickness.
  • the compressed material 43 is made.
  • the metal powder mixture 40 is put into a predetermined mold, and the metal powder compact 43 is produced by press working in which the mold is pressed (pressed) by a press machine.
  • the press pressure (pressure) during the press working is in the range of 500 MPa to 800 MPa.
  • the pressing pressure pressure
  • the metal powder mixture 40 is pressurized (compressed) at a pressure in the above range to produce a metal powder compact 43 having a predetermined hardness, and the metal powder compact 43 is fired.
  • the alloy molded product 44 having a predetermined hardness can be produced, and the alloy molded product 44 can be finely pulverized to produce the alloy powder 13 having a predetermined particle size.
  • the Ni powder 42, the Ni powder 42, the Cu (copper) powder 42, and the ZN (zinc) powder 42 A predetermined amount of the mixed metal powder mixture 40 is put into a mold, and the metal powder mixture 40 is pressed by press working to compress the metal powder mixture 40 and have a predetermined area and a predetermined thickness of the metal powder compressed material 43. make.
  • a predetermined amount of a metal powder mixture 40 obtained by mixing Ni powder 42, Mn (manganese) powder 42, and Mo (molybdenum) powder 42 is charged into a mold, and the metal powder mixture 40 is charged.
  • a pressed metal powder mixture 43 having a predetermined area and a predetermined thickness is produced by pressing the metal powder mixture 40 by pressing.
  • the compressed metal powder production step S3 in the compressed metal powder 41 containing Fe (iron) as a main component, powder of Fe 42, powder of Ni (nickel) 42, powder of Cu (copper) 42 A predetermined amount of the metal powder mixture 40 mixed with the metal powder mixture is charged into a mold, and the metal powder mixture 40 is pressed by press working to compress the metal powder mixture 40 and have a predetermined area and a predetermined thickness.
  • Make 43 Alternatively, a predetermined amount of a metal powder mixture 40 obtained by mixing Fe powder 42, Ti (titanium) powder 42, and Ag (silver) powder 42 is charged into a mold, and the metal powder mixture 40 is charged.
  • a pressed metal powder mixture 43 having a predetermined area and a predetermined thickness is produced by pressing the metal powder mixture 40 by pressing.
  • the metal powder compact creation step S3 in the metal powder compact 41 containing Cu (copper) as a main component, a Cu powder 42, an Fe (iron) powder 42, and a Zn (zinc) powder 42 A predetermined amount of the metal powder mixture 40 in which the metal powder mixture 40 is mixed is put into a mold, and the metal powder mixture 40 is pressed (compressed) by press working to compress the metal powder mixture 40 into a metal having a predetermined area and a predetermined thickness.
  • a powder compact 43 is made.
  • a predetermined amount of a metal powder mixture 40 obtained by mixing Cu powder 42, Fe (iron) powder 42, and Ag (silver) powder 42 is charged into a mold, and the metal powder mixture 40 is charged.
  • a pressed metal powder mixture 43 having a predetermined area and a predetermined thickness is produced by pressing the metal powder mixture 40 by pressing.
  • the metal powder compressed product 43 produced in the metal powder compressed product preparation process S3 is charged into a furnace (steam superheater, electric furnace, or the like), and the metal powder compressed product 43 is placed in the furnace.
  • a furnace steam superheater, electric furnace, or the like
  • the metal powder compressed product 43 is placed in the furnace.
  • an alloy molded article 44 having a porous structure in which a number of fine flow paths (passage holes) having an opening diameter in a range of 1 ⁇ m to 100 ⁇ m is formed.
  • the compressed metal powder 43 is fired for a long time at a temperature at which at least two transition metals 41 among the at least three transition metals 41 selected in the transition metal selection step S1 are melted.
  • the firing (sintering) time is 3 hours to 6 hours.
  • the metal powder compact 43 compressed to a predetermined area and a predetermined thickness powders 42 of at least two types of transition metals 41 are melted, and the molten transition metal 41 is bound with a binder. Then, the powder 42 of another transition metal 41 is joined (fixed).
  • the Ni powder 42, the Cu (copper) powder 42, and the ZN (zinc) powder 42 were mixed in the compressed metal powder 41 mainly containing Ni (nickel).
  • a metal powder compact 43 obtained by compressing the metal powder mixture 40 is fired in a furnace for a long time to form an alloy molded article having a porous structure in which a number of fine channels (passage holes) having an opening diameter in a range of 1 ⁇ m to 100 ⁇ m are formed.
  • Make 44 In an alloy molded article 44 formed from the Ni powder 42, the Cu powder 42, and the Zn powder 42, the metal powder is heated at a temperature (for example, 1100 ° C. to 1200 ° C.) at which the Zn and Cu powder 42 is melted.
  • the compact 43 is fired (sintered), and the Ni powder 42 is joined (fixed) by the molten Zn and Cu powder 42.
  • An alloy molding 44 is made.
  • the metal powder is melted at a temperature at which the Mn and Ni powder 42 is melted (for example, 1460 ° C to 1500 ° C).
  • the body compact 43 is fired, and the Mo powder 42 is joined (fixed) by the molten Mn and Ni powder 42.
  • the metal powder compact 41 containing Fe (iron) as a main component a powder 42 of Fe, a powder 42 of Ni (nickel), and a powder 42 of Cu (copper) are mixed.
  • Metal powder compact 43 obtained by compressing the compressed metal powder mixture 40 is baked in a furnace for a long time to form a porous alloy having a large number of fine channels (passage holes) having an opening diameter in the range of 1 ⁇ m to 100 ⁇ m.
  • the metal powder is heated at a temperature (for example, 1460 ° C. to 1500 ° C.) at which the Cu and Ni powders 42 are melted.
  • the body compact 43 is fired, and the Fe powder 42 is joined (fixed) by the molten Cu and Ni powder 42.
  • the powdered Fe powder 41 mainly composed of Fe (iron) contains the powder 42 of Fe, the powder 42 of Ti (titanium), and the powder 42 of Ag (silver). Is pressed in a furnace for a long time to form a metal powder mixture 40 obtained by compressing a metal powder mixture 40, and a porous structure having a large number of fine channels (passage holes) having an opening diameter in the range of 1 ⁇ m to 100 ⁇ m.
  • An alloy molding 44 is made. In an alloy molding 44 formed from the Fe powder 42, the Ti powder 42, and the Ag powder 42, the metal powder is melted at a temperature at which the Ag and Fe powder 42 is melted (for example, 1540 ° C. to 1600 ° C.). The body compact 43 is fired, and the Ti powder 42 is joined (fixed) by the molten Ag and Fe powder 42.
  • the Cu powder 42, the Fe (iron) powder 42, and the Zn (zinc) powder 42 are mixed in the compressed metal powder 41 mainly containing Cu (copper).
  • Metal powder compact 43 obtained by compressing the compressed metal powder mixture 40 is baked in a furnace for a long time to form a porous alloy having a large number of fine channels (passage holes) having an opening diameter in the range of 1 ⁇ m to 100 ⁇ m.
  • the metal powder is melted at a temperature at which the Zn and Cu powder 42 is melted (for example, 1090 ° C. to 1200 ° C.).
  • the body compact 43 is fired, and the Fe powder 42 is joined (fixed) by the molten Zn and Cu powder 42.
  • the compressed metal powder 41 containing Cu (copper) as a main component includes a powder 42 of Cu, a powder 42 of Fe (iron), and a powder 42 of Ag (silver).
  • the metal powder mixture 43 obtained by compressing the metal powder mixture 40 which is obtained by baking the mixture in a furnace for a long time to form a porous structure having a large number of fine channels (passage holes) having an opening diameter in the range of 1 ⁇ m to 100 ⁇ m.
  • An alloy molding 44 is made.
  • the metal powder is melted at a temperature at which the Ag and Cu powder 42 are melted (for example, 1090 ° C. to 1200 ° C.).
  • the body compact 43 is fired, and the Fe powder 42 is bonded (fixed) by the molten Ag and Cu powder 42.
  • the alloy powder 44 produced in the alloy molded article preparation step S4 is finely pulverized by a pulverizer to a particle size of 10 ⁇ m to 200 ⁇ m to produce the alloy powder 13.
  • a pulverizer As an example of an alloy powder 13 containing Ni (nickel) as a main component (an alloy powder containing Ni as a main component), Ni powder 42, Cu powder 42, and ZN powder 42 are uniformly mixed.
  • a metal powder compact 43 obtained by compressing the dispersed metal powder mixture 40 is fired to form an alloy molded product 44, and the alloy molded product 44 is finely pulverized by a pulverizer to a particle size of 10 ⁇ m to 200 ⁇ m. Things.
  • alloy powder 13 containing Ni (nickel) as a main component is a metal powder mixture 40 in which Ni powder 42, Mn powder 42, and Mo powder 42 are uniformly mixed and dispersed.
  • the compacted metal powder compact 43 is fired to form an alloy compact 44, and the alloy compact 44 is finely pulverized by a fine pulverizer to a particle size of 10 ⁇ m to 200 ⁇ m.
  • an alloy powder 13 containing Fe (iron) as a main component an alloy powder containing Fe as a main component
  • a powder 42 of Fe, a powder 42 of Ni, and a powder 42 of Cu are uniformly mixed.
  • a metal powder compact 43 obtained by compressing the dispersed metal powder mixture 40 is fired to form an alloy molded product 44, and the alloy molded product 44 is finely pulverized by a pulverizer to a particle size of 10 ⁇ m to 200 ⁇ m. Things.
  • Another example of the alloy powder 13 containing Fe (iron) as a main component is a metal powder mixture 40 in which Fe powder 42, Ti powder 42, and Ag powder 42 are uniformly mixed and dispersed.
  • the compacted metal powder compact 43 is fired to form an alloy compact 44, and the alloy compact 44 is finely pulverized by a fine pulverizer to a particle size of 10 ⁇ m to 200 ⁇ m.
  • an alloy powder 13 containing Cu (copper) as a main component an alloy powder containing Cu as a main component
  • a Cu powder 42, an Fe powder 42, and a Zn powder 42 are uniformly mixed.
  • a metal powder compact 43 obtained by compressing the dispersed metal powder mixture 40 is fired to form an alloy molded product 44, and the alloy molded product 44 is finely pulverized by a pulverizer to a particle size of 10 ⁇ m to 200 ⁇ m. Things.
  • a metal powder mixture 40 in which Cu powder 42, Fe powder 42, and Ag powder 42 are uniformly mixed and dispersed is used.
  • the compacted metal powder compact 43 is fired to form an alloy compact 44, and the alloy compact 44 is finely pulverized by a fine pulverizer to a particle size of 10 ⁇ m to 200 ⁇ m.
  • the plurality of alloy powders 13 produced in the alloy powder producing step S5 are combined with the entire area of the front surface 15 of the carbon electrode plate 14 having a predetermined area and a thickness L1 of 0.03 mm to 0.3 mm. It is carried on the entire area of the rear surface 16 (the entire area on both sides).
  • the alloy powders 13 are provided with a predetermined area and 0.03 mm to 0.3 mm so that the plurality of alloy powders 13 are overlapped (laminated) in the thickness direction of the carbon electrode plate 14.
  • the previously described alloy powder laminated porous structure 17 is formed.
  • the alloy powder 13 is supported on both surfaces of the carbon electrode plate 14 by a conductive binder (conductive binder) or plasma spraying.
  • the electrode manufacturing method includes at least three of the various transition metals 41 such that the composite work function of the work functions of the at least three types of transition metals 41 selected from the various transition metals 41 approximates the work function of the platinum group element.
  • Electrodes 10A and 10B can be made.
  • the alloy powder 13 is supported on the entire area of the front surface 15 and the entire area of the rear surface 16 of the carbon electrode plate 14 having a thickness L1 in the range of 0.03 mm to 0.3 mm. Since the electrode 10B provided with the electrode 10A or the alloy powder laminated porous structure 17 in which a plurality of alloy powders 13 are overlapped can be formed, the electric resistance of the electrodes 10A and 10B can be reduced, Electrodes 10A and 10B are capable of generating sufficient electricity in the fuel cell 21 and supplying sufficient electric energy to the load 29 connected to the fuel cell 21. The electrode 10B can be formed, and the electrolysis can be efficiently performed in the hydrogen gas generator 30. It can make electrodes 10A and the electrode 10B that can generate a large amount of hydrogen gas between.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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Abstract

Le problème décrit par la présente invention est de fournir, sans utiliser d'élément du groupe du platine, une électrode qui peut exercer une activité catalytique (action catalytique) similaire à celle d'une électrode contenant un élément du groupe du platine. À cet effet, l'invention porte sur une électrode (10A) qui est formée à partir : d'une poudre d'alliage (13) obtenue par broyage fin d'un produit moulé en alliage préparé par cuisson d'un corps comprimé d'un mélange de poudres métalliques dans lequel des poudres d'au moins trois types de métaux de transition choisis parmi des métaux de transition de divers types sont mélangées et dispersées de manière uniforme ; et d'une plaque d'électrode en carbone (14) soutenant la poudre d'alliage (13) sur ses deux surfaces et ayant une zone prédéterminée. Au moins trois types de métaux de transition sont sélectionnés pour le mélange de poudres métalliques parmi les métaux de transition de divers types, de telle sorte que la fonction de travail combinée des fonctions de travail desdits trois types sélectionnés de métaux de transition s'approche de la fonction de travail d'un élément du groupe du platine.
PCT/JP2019/028393 2018-07-19 2019-07-19 Électrode et procédé de fabrication d'électrode WO2020017623A1 (fr)

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Citations (6)

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JPS5973848A (ja) * 1982-10-19 1984-04-26 Showa Denko Kk 燃料電池の電極用炭素多孔板の製造法
JPH11185771A (ja) * 1997-12-25 1999-07-09 Osaka Gas Co Ltd 抄紙体および燃料電池用多孔質炭素板の製造方法
JP2004207088A (ja) * 2002-12-26 2004-07-22 Nissan Motor Co Ltd ガス透過性基体及びこれを用いた固体酸化物形燃料電池
JP2008016338A (ja) * 2006-07-06 2008-01-24 Toyota Motor Corp 燃料電池、多孔質白金シート、および、燃料電池の製造方法
JP2017098004A (ja) * 2015-11-20 2017-06-01 株式会社健明 燃料電池用電極材料、およびその製造方法
JP2017095746A (ja) * 2015-11-20 2017-06-01 鈴木　健治 水素生成装置および給湯システム

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5973848A (ja) * 1982-10-19 1984-04-26 Showa Denko Kk 燃料電池の電極用炭素多孔板の製造法
JPH11185771A (ja) * 1997-12-25 1999-07-09 Osaka Gas Co Ltd 抄紙体および燃料電池用多孔質炭素板の製造方法
JP2004207088A (ja) * 2002-12-26 2004-07-22 Nissan Motor Co Ltd ガス透過性基体及びこれを用いた固体酸化物形燃料電池
JP2008016338A (ja) * 2006-07-06 2008-01-24 Toyota Motor Corp 燃料電池、多孔質白金シート、および、燃料電池の製造方法
JP2017098004A (ja) * 2015-11-20 2017-06-01 株式会社健明 燃料電池用電極材料、およびその製造方法
JP2017095746A (ja) * 2015-11-20 2017-06-01 鈴木　健治 水素生成装置および給湯システム

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