[go: up one dir, main page]

WO1999066575A1 - Procede servant a fabriquer une electrode composite de catalyseur electrolytique en polymere solide et pile a combustible - Google Patents

Procede servant a fabriquer une electrode composite de catalyseur electrolytique en polymere solide et pile a combustible Download PDF

Info

Publication number
WO1999066575A1
WO1999066575A1 PCT/JP1999/003226 JP9903226W WO9966575A1 WO 1999066575 A1 WO1999066575 A1 WO 1999066575A1 JP 9903226 W JP9903226 W JP 9903226W WO 9966575 A1 WO9966575 A1 WO 9966575A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
polymer electrolyte
solid polymer
compound
raw material
Prior art date
Application number
PCT/JP1999/003226
Other languages
English (en)
Japanese (ja)
Inventor
Shuji Hitomi
Original Assignee
Japan Storage Battery Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Japan Storage Battery Co., Ltd. filed Critical Japan Storage Battery Co., Ltd.
Publication of WO1999066575A1 publication Critical patent/WO1999066575A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for producing a solid polymer electrolyte-catalyst composite electrode used for a fuel cell, a hydroelectric battery, and the like, and a fuel cell using the electrode produced by the method.
  • Solid polymer electrolyte fuel cells and solid polymer electrolyte water electrolyzers use, for example, an ion exchange membrane such as a perfluorosulfonate membrane as an electrolyte, and have an anode and a cathode on both sides of the ion exchange membrane.
  • the electrodes are joined together, and a solid polymer electrolyte-catalyst composite electrode is used as these electrodes.
  • a solid polymer electrolyte-catalyst composite electrode refers to an electrode composed of a solid polymer electrolyte and a catalyst substance.
  • the solid polymer electrolyte-catalyst composite electrode used above is composed of a solid polymer electrolyte and catalyst particles.
  • a paste composed of a dissolved solid polymer electrolyte solution and catalyst particles is formed on a polymer film (generally a thickness of 3 to 30 ⁇ m), and then heated and dried. You.
  • a PTFE (polytetrafluoroethylene) particle dispersion may be added to the paste as needed.
  • the catalyst particles function as an electron conduction channel
  • the solid polymer electrolyte functions as a proton conduction channel
  • the pores formed in the electrode function as supply and discharge channels for the active material and the product.
  • the output voltage of a fuel cell is expressed as follows.
  • the catalyst material supported on the electrode should be as high as possible suitable for each reaction. Must be active. However, the higher the activity of the catalyst particles, the more dangerous the manufacturing process of the solid polymer electrolyte-catalyst composite electrode.
  • the solid polymer electrolyte is actuated by the action of the catalyst particles. The alcohol in the electrolyte solution reacts with the oxygen in the air to generate heat, which can cause ignition.
  • a method for ensuring safety for example, a method of preparing a paste in a nitrogen atmosphere, or a method in which the catalyst particles are wetted in advance with water so that the catalyst particles do not come into direct contact with air.
  • a method is used in which a paste is prepared using catalyst particles pre-moistened with water, which can use a simpler manufacturing apparatus than the former method.
  • the present invention relates to a method for producing a solid polymer electrolyte-catalyst composite electrode capable of supporting a catalyst substance in a solid polymer electrolyte-catalyst composite electrode with simple equipment, safely, and having as large an activity as possible.
  • the purpose is to provide.
  • the method of the present invention focuses on the fact that a catalytic substance such as a metal having a high catalytic activity also has a low catalytic activity in a compound thereof, and furthermore, a mixture of a solid polymer electrolyte and the above compound. It has been found that by reduction, the compound can be reduced to produce a catalytic substance.
  • the solid polymer electrolyte is quickly adsorbed on the catalytic substance obtained by the reduction, and the protective effect is obtained.
  • the discovery that the catalytic substances generated by the reduction are prevented from coming into direct contact with each other to prevent aggregation of the generated catalytic substances.
  • a mixture of a catalyst raw material compound and a solid polymer electrolyte is prepared, and the catalyst raw material compound in the mixture is chemically reduced.
  • the method for producing a solid polymer electrolyte-catalyst composite electrode of the present invention is a method for producing a solid polymer electrolyte-catalyst composite electrode comprising a solid polymer electrolyte and a catalyst substance.
  • a mixture of a catalyst raw material compound to be produced and a solid polymer electrolyte is prepared, and the catalyst raw material compound in the mixture is chemically reduced.
  • FIG. 1 is a diagram showing current-voltage characteristics of cells A and B
  • FIG. 2 is a diagram showing current-voltage characteristics of cells C and D
  • FIG. 3 is a diagram showing current-voltage characteristics of cells E and F.
  • the solid polymer electrolyte-catalyst composite electrode to which the production method of the present invention is applied is an electrode composed of a solid polymer electrolyte and a catalyst substance, for example, a solid polymer electrolyte and a catalyst.
  • This electrode is used as a fuel cell or a water electrolyzer, for example, by being joined to both surfaces of an ion exchange membrane and further providing a power feeder thereon.
  • the catalyst raw material compound used in the production method of the present invention is a compound that can be a catalyst substance when the compound is reduced. If the catalyst substance functions as a catalyst, its shape, etc. Although the form of the catalyst substance is not particularly limited, for example, a substance that generates catalytic metal particles by reduction is used. The function as a catalyst is selected according to its use.For example, for fuel cells, those with high oxygen reduction capacity and hydrogen oxidation capacity, and for water electrolysis tanks, water oxidation capacity Those with high proton reduction ability are selected.
  • platinum group metals such as platinum, rhodium, ruthenium, iridium, palladium, and osmium are suitable as catalyst materials, and a solid polymer electrolyte-catalyst composite comprising these catalyst materials and a solid polymer electrolyte is manufactured.
  • a platinum group metal compound such as platinum, rhodium, ruthenium, iridium, palladium, or osmium
  • the compound has a metal salt form.
  • chlorides of platinum group metals are preferred.
  • a metal compound When a metal compound is used, a mixture of several compounds may be used, or a complex or a double salt may be used. For example, by using a mixture of a platinum compound and a ruthenium compound, a platinum-ruthenium alloy can be formed by a reduction step.
  • the mixture of the catalyst raw material compound and the solid polymer electrolyte may be in a liquid, solid or misaligned form as long as the catalyst raw material compound and the solid polymer electrolyte are mixed. It is preferable to use a porous body prepared by dispersing a catalyst raw material compound in a base made of a solid polymer electrolyte having a shape or the like, and to use such a porous body.
  • a paste consisting of a catalyst raw material compound and a PTFE particle dispersion solution is formed into a film (preferably fliff 3 to 3 ⁇ ) on a polymer film, heated and dried, and then a solid polymer electrolyte solution is applied and impregnated. , Let it dry,
  • a paste comprising a catalyst raw material compound, a solid polymer electrolyte solution, and, if necessary, a PTFE particle dispersion solution is applied onto a conductive porous carbon electrode substrate, and heated and dried.
  • a paste consisting of a catalyst raw material compound and a PTFE particle dispersion is applied to a conductive porous electrode substrate, heated and dried, and then a solid polymer electrolyte solution is applied, impregnated, and dried. It is preferable that it is produced by
  • carbon particles may be added to the above-mentioned paste, in which case the carbon particles play a role in forming the above-mentioned electron conduction channel.
  • a mixture of the catalyst raw material compound and the solid polymer electrolyte may be bonded to both sides or one side of the ion exchange membrane.
  • the solid polymer electrolyte is preferably made of an ion exchange resin, and is preferably a sulfonic acid type polymer solid electrolyte of perfluorosulfonic acid or styrene-divinylbenzene.
  • the catalyst raw material compound and the solid polymer electrolyte must be mixed before the reduction treatment. It is preferable to sufficiently evaporate the solvent of the solid polymer electrolyte such as alcohol in the mixture.
  • a chemical reduction method using a reducing agent suitable for mass production, borohydride compound such as NaBH 4, alkyl borane or ⁇ 2 ⁇ 4 ⁇ ⁇ 2 0 such as dimethyl Chiruaminboran, N 2 H 6 Reduction in the liquid phase using a reducing solution consisting of a reducing agent such as hydrazine hydrate or hydrazine compound such as Cl2 and a solvent such as water or alcohol, or reduction in the gas phase using hydrogen gas, Alternatively, reduction in the gas phase using an inert gas containing hydrazine can be used. Particularly, when manufacturing an electrode for a fuel cell, hydrogen gas or water is used.
  • K 2 PtCl 6 or K 2 IrCl 6 is used as a catalyst raw material compound.
  • a method of reducing the catalyst raw material compound using a reducing solution containing a boron compound using an alcohol having extremely low solubility of the catalyst raw material compound is preferable.
  • the present invention will be described in further detail by describing a method for producing an electrode for a solid polymer electrolyte fuel cell including a catalyst material composed of two or more metal elements and a solid polymer electrolyte.
  • Solid polymer electrolyte fuel cells operate at relatively low temperatures and have high energy-efficiency, so they are expected to be used, for example, as power sources for electric vehicles.
  • Oxidant such as oxygen is supplied to fuel and cathode to generate electricity by electrochemical reaction.
  • DMFC direct methanol fuel cell
  • platinum catalysts commonly used in PEFCs usually have low activity for electrochemical oxidation of methanol, so alloy catalysts containing platinum group metals, such as Pt-Ru alloy Particles of Pt and Sn alloys are used as catalyst materials.
  • methanol is used as the primary fuel
  • a reformer utilizing the chemical reaction between methanol and water is used to supply hydrogen, which is obtained by reforming methanol as needed.
  • the fuel cell used in such a method is called a fuel cell reformed fuel cell.
  • Hydrogen sent to a methanol reformed fuel cell often contains about 10 Oppm of CO, so in this fuel cell, the platinum catalyst commonly used for PEFC is greatly affected by CO poisoning. Since no output can be obtained, an alloy catalyst containing a platinum group metal with high resistance to CO poisoning, for example, particles of a Pt—: Ru alloy is used as the catalyst material.
  • a catalyst substance composed of two or more elements such as an alloy.
  • the catalyst particles and the solid polymer electrolyte described above are combined.
  • the production method of the present invention particularly exhibits its usefulness, and when a catalyst substance comprising two or more elements such as an alloy catalyst is used, simple and safe, and small catalyst particles are uniformly dispersed. It enables the production of a solid polymer electrolyte-catalyst composite electrode. That is, when producing a solid polymer electrolyte-catalyst composite electrode composed of a catalyst material composed of two or more elements and a solid polymer electrolyte, a mixture of two or more catalyst raw material compounds and a solid polymer electrolyte is used. Prepare and chemically reduce these two or more catalyst raw material compounds.
  • the catalyst particles include alloy catalyst particles composed of two or more elements and a solid polymer electrolyte, and the catalyst particles are three-dimensionally distributed in the solid polymer electrolyte and internally.
  • a porous electrode with multiple pores, an electron conduction channel formed by highly active catalyst particles, a proton conduction channel formed by a solid electrolyte, and an active material formed by a large number of pores is manufactured.
  • the catalyst substance composed of two or more metal elements refers to alloy particles or mixture particles of a solid solution or an intermetallic compound composed of two or more metal elements.
  • the two or more catalyst raw material compounds used in this case are compounds that can be converted into a catalyst substance composed of two or more metal elements by reducing these compounds.
  • catalytic substance a substance having high oxygen reducing ability, hydrogen or CO or methanol oxidizing ability is selected, and such catalytic substances include platinum (Pt), rhodium.
  • Platinum group metals such as (Ru), ruthenium (Ru), iridium (Ir), palladium (Pd), and osmium are suitable.
  • the catalyst raw material compound it is preferable to use a platinum group metal compound such as platinum, rhodium, ruthenium, iridium, palladium, and osmium, and among these, a compound having a metal salt form as a compound is preferable.
  • a platinum group metal compound such as platinum, rhodium, ruthenium, iridium, palladium, and osmium
  • a compound having a metal salt form is preferable.
  • Preferred are, for example, chlorides of platinum group metals.
  • At least one of the two or more catalyst raw material compounds when preparing an electrode, when preparing an electrode with improved electrochemical oxidation reaction performance of methanol, such as an electrode for DMFC, at least one of the two or more catalyst raw material compounds must be a platinum group element. It is preferable to include More preferably, at least one of the two or more catalyst raw material compounds contains an element selected from the group consisting of Pt, Ru, Rh, Pd, and Ir. In these cases, in particular, it is preferable that at least two compounds of the catalyst raw material contain at least a compound of platinum and ruthenium, or that two or more catalyst raw materials are used. It is preferable that the compound contains at least a compound of iridium and a compound of ruthenium.
  • the mixture of two or more catalyst raw material compounds and the solid polymer electrolyte has a liquid / solid state when the two or more catalyst raw material compounds and the solid polymer electrolyte are mixed.
  • a mixture in which a catalyst raw material compound is dispersed in a matrix composed of a solid polymer electrolyte is made up of a paste comprising two or more catalyst raw material compounds, a solid polymer electrolyte solution, and, if necessary, a PTFE particle dispersion solution. It is formed on a film (preferably ⁇ 30 ⁇ m) and dried by heating.
  • a paste comprising two or more catalyst raw material compounds and a PTFE particle dispersion solution is formed on a polymer film (preferably, J3Iff 3 to 30 m), dried by heating, and then the solid polymer electrolyte solution is dried. After applying, impregnating and drying,
  • a paste consisting of two or more catalyst raw material compounds, a solid polymer electrolyte solution, and, if necessary, a PTFE particle dispersion solution is applied to a conductive porous carbon substrate and heated. Dry,
  • a paste consisting of two or more catalyst raw material compounds and a PTFE particle dispersion solution is applied to a conductive porous carbon electrode, heated and dried, and then a solid polymer electrolyte solution is applied and impregnated. After that, it is preferable to produce it by drying.
  • carbon particles may be added to each of the above-described pastes, if necessary. In such a case, carbon particles serve to form the above-described electron conduction channel. Furthermore, a form in which a mixture of two or more catalyst raw material compounds and a solid polymer electrolyte is bonded to both sides or one side of the ion exchange membrane may be used.
  • the solid polymer electrolyte is preferably made of an ion exchange resin, and is preferably a sulfonic acid type polymer solid electrolyte of perfluorosulfonic acid or styrene-divinylbenzene.
  • the catalyst raw material compound and the solid It is preferable to carry out the reaction after sufficiently evaporating the solvent of the solid polymer electrolyte such as alcohol in the mixture with the polymer electrolyte. It is preferable to use a chemical reduction method using a reducing agent suitable for mass production, such as a borohydride such as NaBH 4 , an alkylamine borane such as dimethylamine borane, or N 2 H 4 ′ H 20.
  • a reducing agent suitable for mass production such as a borohydride such as NaBH 4 , an alkylamine borane such as dimethylamine borane, or N 2 H 4 ′ H 20.
  • N 2 reducing agent such as H 6 C1 2 hydrazine hydrate or hydrazine compounds such as water or alcohol - reduction with liquid phase with a reducing solution comprising a solvent such as Le, or hydrogen gas or hydrogen Reduction in the gas phase using a gas containing gas or reduction in the gas phase using an inert gas containing hydrazine
  • a reducing solution comprising a solvent such as Le, or hydrogen gas or hydrogen Reduction in the gas phase using a gas containing gas or reduction in the gas phase using an inert gas containing hydrazine
  • a reduction method in a gas phase in which reduction is performed with an inert gas containing hydrazine is preferable because the obtained catalyst substance has higher dispersion and fine particles than a catalyst substance obtained by a reduction method in a liquid phase.
  • reduction conditions such as reduction temperature and pressure are selected so that two or more catalyst raw material compounds are reduced simultaneously. Is preferred.
  • the reduction temperature and pressure should be changed over time so that two or more catalyst raw material compounds are sequentially reduced. Is preferred.
  • a reformed fuel cell or a direct fuel cell can be a very efficient fuel cell.
  • K 2 PtCl 6 chloroplatinic acid power rim
  • solid polymer electrolyte solution Aldrich Co., Nafion 5 wt./. Solution
  • PTFE particles Mitsubishi Fluorochemical Co., Ltd., Teflon 30 J, average particle size 0.23 ⁇ (01) was applied on a conductive porous electrode substrate (0.5 mm) of water-repellent conductive porous material, and dried at 120 ° C for 1 hour in a nitrogen atmosphere.
  • Example electrode A the platinum amount of the electrode A was about 4 mg / cm 2 .
  • the amount of platinum black was adjusted so that the amount of platinum of the comparative example electrode B was about 4 mg / cm 2 .
  • Example electrode A and comparative example electrode B were bonded to both surfaces of an ion exchange membrane (made by DuPont, trade name: Naphion, film thickness: about 50 m) by hot pressing (140 ° C), respectively.
  • Fig. 1 shows the current-voltage characteristics when cells A and B are assembled into a single fuel cell and hydrogen and oxygen (2 atm, 80 ° C) are supplied to these cells. From the figure, it can be seen that the cell A according to the present invention shows a higher output voltage than the conventional cell B, although it is easily manufactured.
  • the electrode of the present invention is made by reducing a mixture of a solid polymer electrolyte and a catalyst raw material compound that is reduced to generate a catalyst substance, and thus the catalyst obtained by reduction of the solid polymer electrolyte is used. This is because they exhibit a protective effect by adsorbing on the particles, prevent the catalyst particles from directly contacting each other, and prevent the particles from aggregating, thereby maintaining high activity.
  • Pt black was agglomerated into particles of 10 to 20 / m in Comparative Example Electrode B, whereas aggregated catalyst particles were observed in Example Electrode A. Absent.
  • K 2 IrCl 6 (potassium iridium dichloride), K 2 PtCl 6 and solid polymer electrolyte solution (Aldrich, Naphion 5 wt% solution) at a weight ratio of 2.0 / 1.0 / 2.77, and mix at 70 ° C After heating and concentrating to obtain a paste having an appropriate viscosity, a film was formed on a FEP (tetrafluoroethylene-hexafluoropropylene copolymer) film and air-dried for 24 hours.
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • the Irijiumu and mixtures of salt and polymer solid electrolyte platinum respect, the implementation of 70 ° C E evening Roh Ichiru solution for water electrolyzer perform reduction treatment of 2 hours in containing NaBH 4 in 0.4 wt% Example electrode C was obtained. Analysis was performed separately, it was confirmed that the amount of supported Irijiu arm and platinum electrode C is about 2 mg / cm 2 and lmg / cm 2, respectively.
  • Iridium powder (Tanaka precious metal, average particle diameter 10 zm) pre-moistened with water, platinum black (Nichi-Chemcat, average particle diameter 1.5 ⁇ ⁇ m) and solid polymer electrolyte solution 0.8 / 0.4 / Mix at a weight ratio of 2.77, heat and concentrate at 70 ° C to obtain a paste with an appropriate viscosity, and then form a film on FEP (tetrafluoroethylene-hexylene hexafluoropropylene copolymer) film for 24 hours. Was dried naturally to obtain Comparative Example Electrode D.
  • Irijiumu powder and platinum black amount as the amount of iridium and platinum is about 2 mg / cm 2 and lmg / cm 2 each of the comparative example electrodes D.
  • Electrode C of Example and Electrode D of Comparative Example were bonded to both sides of an ion exchange membrane (DuPont, Nafion, Mi-approximately 50 m) by hot pressing (140 ° C) and assembled into a single cell of hydroelectric power. C and D were obtained.
  • Figure 2 shows the current-voltage characteristics of these cells at 80 ° C. From the figure, it can be seen that the cell according to the present invention has a lower electrolysis voltage than the conventional cell.
  • the electrode of the present invention is made by reducing a mixture of a solid polymer electrolyte and a compound of a metal exhibiting catalytic activity, so that the solid polymer electrolyte is adsorbed on the catalyst particles obtained by the reduction. Shows a protective effect, and the catalyst particles come into direct contact with each other This is because they prevent aggregation and maintain high activity.
  • Example Electrode C In addition, as a result of microscopic observation, it was observed that the catalyst particles were agglomerated into particles of 30 to 50 m in Comparative Example Electrode D, but no agglomerated catalyst particles were observed in Example Electrode C.
  • Water-repellent conductive porous paste made of a mixture of potassium chloroplatinate (K 2 PtCl 6 ), ruthenium chloride (RuCl 3 ), and a solid polymer electrolyte solution (Aldrich, Naphion 5 wt% solution) It was applied on a porous carbon substrate (0.5 mm) and dried at 120 ° C for 1 hour in a nitrogen atmosphere.
  • Example electrode E a mixture of the above K 2 Pt Cl 6 , ruthenium chloride (RuCl 3 ) and a solid polymer electrolyte solution was reduced in a hydrogen atmosphere at 200 ° C. and 1 atm for 4 hours to obtain Example electrode E.
  • the amount of platinum and the amount of ruthenium of the electrode E were about 3 mg / cm 2 respectively.
  • a conductive porous material with water repellency obtained by mixing a paste in which Pt_Ru0X fine powder pre-wetted with water and a solid polymer electrolyte solution (Aldrich Co., Ltd., Naphion 5 wt% solution) are mixed.
  • a paste in which Pt_Ru0X fine powder pre-wetted with water and a solid polymer electrolyte solution (Aldrich Co., Ltd., Naphion 5 wt% solution) were mixed.
  • a carbon electrode substrate 0.5 mm
  • Comparative Example Electrode F Comparative Example Electrode F.
  • the amount of platinum black was adjusted so that the amount of platinum and the amount of ruthenium of the comparative electrode F were about 3 mg / cm 2 respectively.
  • the electrode E of Example and the electrode F of Comparative Example were hot-pressed (140 ° C) on both sides of an ion-exchange membrane (made by DuPont, trade name: Naphion, film thickness: approx.
  • the cells were joined and assembled into a single cell of a fuel cell to obtain cells E and F.
  • Figure 3 shows the current-voltage characteristics when hydrogen containing 10 Oppm of CO was supplied as fuel to these cells and oxygen (2 atm, 80 ° C) was supplied as oxidant. From the figure, it can be seen that the cell E according to the present invention has good resistance to CO poisoning and shows a higher output voltage than the conventional cell F, although it is easily manufactured.
  • the electrode of the present invention is a catalyst raw material compound which is reduced to produce a catalyst substance and a solid.
  • the solid polymer electrolyte is adsorbed on the catalyst particles obtained by the reduction, and the catalyst particles come into direct contact with each other to aggregate the particles. This is because the catalyst particles maintain high activity.
  • a solid polymer composed of a solid polymer electrolyte and a catalyst substance is safely and easily exhibited by a simple device without hindering the catalytic activity of the catalyst substance.
  • An electrolyte-catalyst composite electrode can be manufactured.
  • the electrode comprising a catalyst material comprising two or more metal elements and a solid polymer electrolyte produced by the present invention is a modified methanol fuel cell or DMFC which requires an alloy catalyst for the oxidation reaction of fuel at the electrode. Is particularly preferable as the anode electrode.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Materials Engineering (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

Procédé servant à fabriquer une électrode composite de catalyseur électrolytique en polymère solide mise en application pour une pile à combustible électrolytique en polymère solide, contenant un électrolyte en polymère solide et des particules catalytiques et possédant une structure poreuse dans laquelle ces particules catalytiques sont distribuées de façon tridimensionnelle, ce qui permet de supporter le matériau catalytique dans l'électrode du catalyseur électrolytique dans un état aussi actif que possible au moyen d'un simple dispositif. On prépare un mélange d'un composé de matériau catalytique qui est un composé d'un métal du groupe platine capable de produire un matériau catalytique quand il est réduit et un électrolyte en polymère solide, puis on effectue la réduction chimique de ce composé de matériau catalytique du mélange au moyen d'un gaz inerte contenant de l'hydrogène gazeux et de l'hydrazine. On utilise, de préférence, une électrode produite au moyen de deux composés de matériau catalytique, par exemple, un composé de platine et un composé de ruthénium, ou un composé d'iridium et un composé de ruthénium, en tant qu'anode de pile à combustible au méthanol modifié ou de pile à combustible au méthanol direct.
PCT/JP1999/003226 1998-06-18 1999-06-17 Procede servant a fabriquer une electrode composite de catalyseur electrolytique en polymere solide et pile a combustible WO1999066575A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP18980598 1998-06-18
JP10/189805 1998-06-18

Publications (1)

Publication Number Publication Date
WO1999066575A1 true WO1999066575A1 (fr) 1999-12-23

Family

ID=16247513

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/003226 WO1999066575A1 (fr) 1998-06-18 1999-06-17 Procede servant a fabriquer une electrode composite de catalyseur electrolytique en polymere solide et pile a combustible

Country Status (1)

Country Link
WO (1) WO1999066575A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002083605A (ja) * 2000-07-29 2002-03-22 Dmc 2 Degussa Metals Catalysts Cerdec Ag Ｐｅｍ−燃料電池用の膜−電極ユニットの製造のためのインキ及びその使用
JP2010055870A (ja) * 2008-08-27 2010-03-11 Nec Corp 触媒ペーストの製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58204188A (ja) * 1982-05-24 1983-11-28 Agency Of Ind Science & Technol イオン交換膜と触媒電極との接合体を製造する方法
JPS61295387A (ja) * 1985-06-21 1986-12-26 Japan Storage Battery Co Ltd イオン交換樹脂膜−電極接合体の製造法
JPH05258755A (ja) * 1991-12-31 1993-10-08 Stonehard Assoc Inc 高分子固体電解質型燃料電池の製造方法
JPH08162122A (ja) * 1994-12-06 1996-06-21 Agency Of Ind Science & Technol 燃料電池用ガス拡散電極の製造方法
JPH0935723A (ja) * 1995-07-20 1997-02-07 Toyota Motor Corp 電極用合金触媒および燃料電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58204188A (ja) * 1982-05-24 1983-11-28 Agency Of Ind Science & Technol イオン交換膜と触媒電極との接合体を製造する方法
JPS61295387A (ja) * 1985-06-21 1986-12-26 Japan Storage Battery Co Ltd イオン交換樹脂膜−電極接合体の製造法
JPH05258755A (ja) * 1991-12-31 1993-10-08 Stonehard Assoc Inc 高分子固体電解質型燃料電池の製造方法
JPH08162122A (ja) * 1994-12-06 1996-06-21 Agency Of Ind Science & Technol 燃料電池用ガス拡散電極の製造方法
JPH0935723A (ja) * 1995-07-20 1997-02-07 Toyota Motor Corp 電極用合金触媒および燃料電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002083605A (ja) * 2000-07-29 2002-03-22 Dmc 2 Degussa Metals Catalysts Cerdec Ag Ｐｅｍ−燃料電池用の膜−電極ユニットの製造のためのインキ及びその使用
JP2010055870A (ja) * 2008-08-27 2010-03-11 Nec Corp 触媒ペーストの製造方法

Similar Documents

Publication Publication Date Title
US6344291B1 (en) Solid polymer electrolyte-catalyst composite electrode, electrode for fuel cell, and process for producing these electrodes
JP5425771B2 (ja) 触媒
US7994088B2 (en) Supported catalyst, method of preparing the same, and fuel cell using the same
JP3649009B2 (ja) 燃料電池用電極およびその製造方法
US20020068213A1 (en) Multiple layer electrode for improved performance
EP2990109A1 (fr) Électrode et la couche de catalyseur d'électrode de pile à combustible la contenant
JP5425765B2 (ja) 触媒層
JP2002110180A (ja) ポリマー電解質−燃料電池用の膜−電極ユニット並びにその製造方法及びその製造のためのインキ
JP2024529245A (ja) 酸素発生反応触媒
JP3649061B2 (ja) 燃料電池用電極およびその製造方法
AU2003253438A1 (en) Conductive carbon, electrode catalyst for fuel cell using the same and fuel cell
JP2007501496A (ja) 界面抵抗を減少させたハイブリッド膜・電極接合体及びその作製方法
JP2001126738A (ja) 燃料電池用電極の製造方法およびそれを用いた直接メタノール燃料電池
EP4374436A1 (fr) Catalyseur de réaction d'évolution d'oxygène
WO1999066575A1 (fr) Procede servant a fabriquer une electrode composite de catalyseur electrolytique en polymere solide et pile a combustible
JP2005222812A (ja) 燃料電池用電極の製造方法
JP2000215899A (ja) 燃料電池用電極の製造方法
JP2006040633A (ja) 燃料電池用電極、その製造方法及びそれを用いた燃料電池
KR20230034949A (ko) 촉매 제조
JP2000012040A (ja) 燃料電池用電極およびその製造方法
JP2003100306A (ja) 固体高分子型燃料電池用電極の製造方法及び固体高分子型燃料電池用電極
JP2001291520A (ja) 燃料電池用電極の製造方法
WO2003069713A1 (fr) Ensembles electrodes a membrane pour cellules electrochimiques
JP2006344424A (ja) 固体高分子形燃料電池用触媒混合体の製造方法
KR20060001320A (ko) 연료전지의 촉매층 형성용 조성물 및 이를 이용한전극막접합체

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase