EP0477246A1 - Process for the manufacture of electrodes for fuel cells - Google Patents

Process for the manufacture of electrodes for fuel cells

Info

Publication number
EP0477246A1
EP0477246A1 EP90909454A EP90909454A EP0477246A1 EP 0477246 A1 EP0477246 A1 EP 0477246A1 EP 90909454 A EP90909454 A EP 90909454A EP 90909454 A EP90909454 A EP 90909454A EP 0477246 A1 EP0477246 A1 EP 0477246A1
Authority
EP
European Patent Office
Prior art keywords
support
foam
sheet
catalyst
powder
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP90909454A
Other languages
German (de)
French (fr)
Inventor
Gérard GAVE
Bernard Bugnet
Robert Rouget
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CENTRE NATIONAL DE RECHERCHES DE SPACIALES
Societe de Recherches et dApplications Electronchimiques SORAPEC SA
SORAPEC SA
Original Assignee
CENTRE NATIONAL DE RECHERCHES DE SPACIALES
Societe de Recherches et dApplications Electronchimiques SORAPEC SA
SORAPEC SA
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 CENTRE NATIONAL DE RECHERCHES DE SPACIALES, Societe de Recherches et dApplications Electronchimiques SORAPEC SA, SORAPEC SA filed Critical CENTRE NATIONAL DE RECHERCHES DE SPACIALES
Publication of EP0477246A1 publication Critical patent/EP0477246A1/en
Withdrawn legal-status Critical Current

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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8668—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8896—Pressing, rolling, calendering
    • 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
    • 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
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0239—Organic resins; Organic polymers
    • 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 the production of electrodes intended to enter into the constitution of fuel cells. Its main object is a process for manufacturing such electrodes and extends to the electrodes obtained by this process.
  • Fuel cells are electro ⁇ chemical cells comprising one or more cells containing an electrolyte between two electrodes, with the particularity that the electricity-producing reaction is a reaction of combustion of a reducing compound with an oxidizing compound, generally the air oxygen.
  • the simplest case involves the formation of hydrogen ions on the anode and their reaction with oxygen on the cathode, with production of water.
  • the invention relates more specifically to the electrodes of fuel cells which involve oxidation-reduction reactions in a three-phase system, where a hydrophobic agent maintains a stable interface, on an active electrode material sodid, with both a gas phase reagent and a liquid electrolyte. It is said that the electrode is then triple contact.
  • the hydrophobic agent used is generally polytetrafluoroethylene, which also plays the role of binder for a catalyst which promotes the oxidation-reduction reaction without otherwise intervening in its result.
  • the hydrophobic binder mixed with the catalyst is formed in the form of a paste with which a conductive grid is coated which collects the current produced.
  • a microporous sheet permeable to the gaseous reagent is applied to the coating layer; it consists of pure polytetrafluoroethylene, containing no catalyst.
  • a similar membrane can be obtained by spraying powdered polytetrafluoroethylene and subjecting the layer obtained to rolling and heat treatment.
  • the present invention essentially aims to improve the performance of electrodes of this kind, by means of a manufacturing process specifically adapted to the use of electrode supports with a very large developed surface, made of metallic foams with high porosity in pores. open.
  • the organic matter itself can be kept in the metal foam or be destroyed by heating and combustion.
  • the subject of the invention is therefore a method of manufacturing a fuel cell electrode, characterized in that an electrode support consisting of a metal foam is used and, for filling said foam with an active mass of catalyst and hydrophobic organic binder, a pulverulent mixture of said catalyst and of said organic binder is put in the form of continuous laminated sheets, at least one such sheet is placed on at least one face of said support, and said sheet is subjected to a pressure on said support to make it penetrate over the majority of its thickness into the pores of the support.
  • the metal foam is a nickel foam, that is to say that the material constituting the support is based on nickel, at least in a surface layer present at the interior of almost all pores, it being understood that there may be underlying layers of another nature.
  • polytetrafluoroethylene as organic binder, and in the laminated sheet prepared for application to the support, the polytetrafluoroethylene is then preferably in a form resulting from the transformation of '' a filamentary powder by fibrillation. It seems that it is thus possible to give the sheet of active mass an optimal flexibility, allowing it to penetrate deep into the metal foam of the support, while nevertheless forming a continuous film lining the surface developed inside the pores. It also appears that by comparison with the previously known techniques, the quantity of hydrophobic organic binder can be significantly reduced compared to the quantity of catalyst, which leads to a better yield of the active mass for a reduced manufacturing cost.
  • the respective dimensions of the metal foam and of the sheet of active mass, as well as the pressing conditions, can be advantageously chosen so that the interpenetration of the sheet into the foam relates to at least 50%, and preferably to practically 70 to 90% of the thickness of the sheet. And to obtain a complete filling of the foam, it is generally advantageous to have two sheets of similar active mass on either side of the support, respectively On two opposite faces of the metal foam, so that each sheet pressed on the face corresponding foam penetrates until joining the other in the middle of the thickness of this foam.
  • the catalyst it may in particular be constituted, in a manner known per se, by a metallic powder based on platinum, palladium, or an alloy of these two metals.
  • powders consisting of carbon grains coated with either a platinum and palladium alloy for the hydrogen electrodes or a gold, platinum and palladium for oxygen electrodes.
  • An electrode obtained by the process of the invention and constituted by the metal foam and the active mass of catalyst and hydrophobic binder having penetrated into the pores, can be used applied against a solid matrix retaining the electrolyte, in particular in a bipolar assembly where two similar electrodes are placed to operate at opposite polarities respectively on each side of the electrolyte matrix and each in contact otherwise with a gas phase reagent.
  • it can also be used in a monopolar assembly, in contact with a liquid electrolyte, in which case the inveation process is advantageously completed to cover the electrode, on the side of the gas phase, d 'a semiporous membrane which forms a barrier impermeable to electrolyte but permeable to gas.
  • the method realizes such a membrane by spraying polytetrafluoroethylene in at least two successive stages, a first from a suspension of polytetrafluoro ⁇ thylene in submicronic microparticles, a second from a granulometry powder of the order of 10 to 50 microns,
  • carrier trode élec ⁇ a nickel foam prepared according to a known process which consists essentially from a foam material * open-pored organic porosity at least equal to 90% in which forms a metallic coating of nickel comprising a sublayer deposited by spraying or evaporation under vacuum and a layer main deposited by electrolysis.
  • submicronic polytetrafluoroethylene in aqueous suspension (registered trademark Teflon of quality 30 N having a particle size of 0.2 micron) with a carbon powder coated with an alloy of platinum and palladium, or of a ternary alloy of gold, platinum and palladium.
  • aqueous suspension registered trademark Teflon of quality 30 N having a particle size of 0.2 micron
  • the active mass is thus prepared in the form of thin, flexible sheets, where the material is continuous, without holes.
  • the polytetrafluoroethylene is in the form of filaments resulting from fibrillation of the powder.
  • a semiporous membrane is then produced in pure polytetrafluoroethylene, without catalyst.
  • the operation is carried out by spraying, in two stages, first using an aqueous suspension of submicron powder (registered trademark Teflon of quality 30 N), then a dry powder having a particle size of approximately 20 microns (registered trademark Teflon, quality 702 ).

Abstract

La présente invention concerne la réalisation d'électrodes destinées à entrer dans la constitution de piles à combustible. Pour fabriquer une telle électrode, on utilise un support d'électrode constitué par une mousse métallique et, pour remplir ladite mousse d'une masse active de catalyseur et de liant organique hydrophobe, on met un mélange pulvérulent dudit catalyseur et dudit liant organique sous forme de feuilles laminées continues, on dispose au moins une telle feuille sur au moins une face dudit support, et l'on soumet ladite feuille à une pression sur ledit support pour la faire pénétrer sur la majorité de son épaisseur dans les pores du support.The present invention relates to the production of electrodes intended to enter into the constitution of fuel cells. To manufacture such an electrode, an electrode support consisting of a metallic foam is used and, to fill said foam with an active mass of catalyst and of hydrophobic organic binder, a pulverulent mixture of said catalyst and of said organic binder is put in the form continuous laminated sheets, at least one such sheet is placed on at least one face of said support, and said sheet is subjected to a pressure on said support to make it penetrate over the majority of its thickness into the pores of the support.

Description

PROCEDE DE FABRICATION D'ELECTRODES DE PILES A COMBUSTIBLEMETHOD FOR MANUFACTURING FUEL CELL ELECTRODES
La présente invention concerne la réalisation d'électrodes destinées à entrer dans la constitution de piles à combustible. Elle a principalement pour objet un procédé de fabrication de telles électrodes et s'étend aux électrodes obtenues par ce procédé.The present invention relates to the production of electrodes intended to enter into the constitution of fuel cells. Its main object is a process for manufacturing such electrodes and extends to the electrodes obtained by this process.
Les piles à combustible sont des piles électro¬ chimiques comprenant une ou plusieurs cellules contenant un électrolyte entre deux électrodes, avec la particularité que la réaction productrice d'électricité est une réaction de combustion d'un composé réducteur par un composé oxydant, généralement l'oxygène de l'air. Le cas le plus simple implique la formation d'ions hydrogène sur l'anode et leur réaction avec l'oxygène sur la cathode, avec production d'eau.Fuel cells are electro¬ chemical cells comprising one or more cells containing an electrolyte between two electrodes, with the particularity that the electricity-producing reaction is a reaction of combustion of a reducing compound with an oxidizing compound, generally the air oxygen. The simplest case involves the formation of hydrogen ions on the anode and their reaction with oxygen on the cathode, with production of water.
Cependant, l'invention s'intéresse plus précisément aux électrodes des piles à combustible qui font intervenir des réactions d'oxydo-réduc ion dans un système à trois phases, où un agent hydrophobe maintient un interface stable, sur un matériau actif d'électrode sodide, avec à la fois un réactif en phase gazeuse et un électrolyte liquide. On dit que l'électrode est alors à triple contact. Dans la pratique, l'agent hydrophobe utilisé est généralement du polytétrafluoréthylène, qui joue également le rôle de liant pour un catalyseur qui favorise la réaction d'oxydo-réduction sans intervenir autrement dans son résultat.However, the invention relates more specifically to the electrodes of fuel cells which involve oxidation-reduction reactions in a three-phase system, where a hydrophobic agent maintains a stable interface, on an active electrode material sodid, with both a gas phase reagent and a liquid electrolyte. It is said that the electrode is then triple contact. In practice, the hydrophobic agent used is generally polytetrafluoroethylene, which also plays the role of binder for a catalyst which promotes the oxidation-reduction reaction without otherwise intervening in its result.
Dans un procédé de réalisation connu d'une telle électrode de pile à combustible, le liant hydrophobe mélangé au catalyseur est rais sous forme d'une pâte dont on enduit une grille conductrice qui collecte le courant produit. En outre, une feuille microporeuse perméable au réactif gazeux est appliquée sur la couche d'enduction ; elle est constituée de polytétrafluoréthylène pur, ne contenant pas de catalyseur. En variante d'une telle feuille, on peut obtenir une membrane similaire en pulvérisant du polytétrafluoréthylène en poudre et en soumettant la couche obtenue à un laminage et un traitement thermique.In a known production method of such a fuel cell electrode, the hydrophobic binder mixed with the catalyst is formed in the form of a paste with which a conductive grid is coated which collects the current produced. In addition, a microporous sheet permeable to the gaseous reagent is applied to the coating layer; it consists of pure polytetrafluoroethylene, containing no catalyst. As a variant of such sheet, a similar membrane can be obtained by spraying powdered polytetrafluoroethylene and subjecting the layer obtained to rolling and heat treatment.
La présente invention vise essentiellement à amé¬ liorer les performances des électrodes de ce genre, grâce à un procédé de fabrication spécifiquement adapté à la mise en oeuvre de supports d'électrode à surface développée très importante, constitués de mousses métalliques à porosité élevée en pores ouverts. On désigne par là notamment des mousses de nickel ou de cuivre qui sont obtenues par des dépôts métalliques réalisés au sein des pores d'une mousse de matière organique à porosité ouverte supérieure à 90 % , et de préférence supérieure à 95 % , que l'on sait produire par exemple par des procédures impliquant un éclatement des pores. La matière organique elle-même peut être conservée dans la mousse métallique ou être détruite par chauffage et combustion.The present invention essentially aims to improve the performance of electrodes of this kind, by means of a manufacturing process specifically adapted to the use of electrode supports with a very large developed surface, made of metallic foams with high porosity in pores. open. This means in particular nickel or copper foams which are obtained by metallic deposits produced within the pores of an organic material foam with open porosity greater than 90%, and preferably greater than 95%, than the it is known to produce, for example, by procedures involving the bursting of pores. The organic matter itself can be kept in the metal foam or be destroyed by heating and combustion.
L'invention a ainsi pour objet un procédé de fabrication d'une électrode de pile à combustible caractérisé en ce que l'on utilise un support d'électrode constitué par une mousse métallique et, pour remplir ladite mousse d'une masse active de catalyseur et de liant orga¬ nique hydrophobe, on met un mélange pulvérulent dudit catalyseur et dudit liant organique sous forme de feuilles laminées continues, on dispose au moins une telle feuille sur au moins une face dudit support, et l'on soumet ladite feuille à une pression sur ledit support pour la faire pénétrer sur la majorité de son épaisseur dans les pores du support.The subject of the invention is therefore a method of manufacturing a fuel cell electrode, characterized in that an electrode support consisting of a metal foam is used and, for filling said foam with an active mass of catalyst and hydrophobic organic binder, a pulverulent mixture of said catalyst and of said organic binder is put in the form of continuous laminated sheets, at least one such sheet is placed on at least one face of said support, and said sheet is subjected to a pressure on said support to make it penetrate over the majority of its thickness into the pores of the support.
Suivant une caractéristique secondaire de l'in¬ vention, la mousse métallique est une mousse de nickel, c'est-à-dire que le matériau constituant le support est à base de nickel, au moins dans une couche de surface présente à l'intérieur de pratiquement tous les pores, étant entendu qu'il peut exister des couches sous-jacentes d'une autre nature. Dans la mise en oeuvre pratique de l'invention, il est avantageux d'utiliser comme liant organique du polytétrafluoréthylène, et dans la feuille laminée préparée pour application sur le support, le polytétrafluoréthylène se trouve alors de préférence sous une forme résultant de la transformation d'une poudre en filaments par fibrillation. Il semble que l'on peut ainsi donner à la feuille de masse active une souplesse optimale, lui permettant de pénétrer en profondeur dans la mousse métallique du support, en formant néanmoins un film continu tapissant la surface développée à l'intérieur des pores. Il apparaît aussi que par comparaison avec les techniques connues antérieurement, on peut diminuer sensiblement la quantité de liant organique hydrophobe par rapport à la quantité de catalyseur, ce qui conduit à un meilleur rendement de la masse active pour un coût de fabrication réduit.According to a secondary characteristic of the invention, the metal foam is a nickel foam, that is to say that the material constituting the support is based on nickel, at least in a surface layer present at the interior of almost all pores, it being understood that there may be underlying layers of another nature. In the practical implementation of the invention, it is advantageous to use polytetrafluoroethylene as organic binder, and in the laminated sheet prepared for application to the support, the polytetrafluoroethylene is then preferably in a form resulting from the transformation of '' a filamentary powder by fibrillation. It seems that it is thus possible to give the sheet of active mass an optimal flexibility, allowing it to penetrate deep into the metal foam of the support, while nevertheless forming a continuous film lining the surface developed inside the pores. It also appears that by comparison with the previously known techniques, the quantity of hydrophobic organic binder can be significantly reduced compared to the quantity of catalyst, which leads to a better yield of the active mass for a reduced manufacturing cost.
Les dimensions respectives de la mousse métallique et de la feuille de masse active, ainsi que les conditions de pressage, peuvent être avantageusement choisies de sorte que l'interpénétration de la feuille dans la mousse porte sur au moins 50 % , et de préférence sur pratiquement 70 à 90 % de l'épaisseur de la feuille. Et pour obtenir un remplissage complet de la mousse, on a en général intérêt à disposer deux feuilles de masse active similaires de part et d'autre du support, respectivement Sur deux faces opposées de la mousse métallique, pour que chaque feuille pressée sur la face correspondante de la mousse pénètre jusqu'à venir rejoindre l'autre au milieu de l'épaisseur de cette mousse.The respective dimensions of the metal foam and of the sheet of active mass, as well as the pressing conditions, can be advantageously chosen so that the interpenetration of the sheet into the foam relates to at least 50%, and preferably to practically 70 to 90% of the thickness of the sheet. And to obtain a complete filling of the foam, it is generally advantageous to have two sheets of similar active mass on either side of the support, respectively On two opposite faces of the metal foam, so that each sheet pressed on the face corresponding foam penetrates until joining the other in the middle of the thickness of this foam.
Quant au catalyseur, il peut être notamment constitué, de manière en soi connue, par une poudre métal¬ lique à base de platine, de palladium, ou d'un alliage de ces deux métaux. Dans la mise en œuvre pratique de l'in- vention, on préfère les poudres constituées de grains de carbone revêtus soit d'un alliage de platine et de palladium pour les électrodes à hydrogène, soit d'un alliage d'or, platine et palladium pour les électrodes à oxygène. - -As for the catalyst, it may in particular be constituted, in a manner known per se, by a metallic powder based on platinum, palladium, or an alloy of these two metals. In the practical implementation of the invention, powders consisting of carbon grains coated with either a platinum and palladium alloy for the hydrogen electrodes or a gold, platinum and palladium for oxygen electrodes. - -
Une électrode obtenue par le procédé de l'invention et constituée par la mousse métallique et la masse active de catalyseur et de liant hydrophobe ayant pénétré dans les pores, peut être utilisée appliquée contre une matrice solide retenant l'électrolyte, notamment dans un ensemble bipolaire où deux électrodes similaires sont placées pour fonctionner à des polarités opposées respectivement de chaque côté de la matrice d'électrolyte et chacune en contact par ailleurs avec un réactif en phase gazeuse.An electrode obtained by the process of the invention and constituted by the metal foam and the active mass of catalyst and hydrophobic binder having penetrated into the pores, can be used applied against a solid matrix retaining the electrolyte, in particular in a bipolar assembly where two similar electrodes are placed to operate at opposite polarities respectively on each side of the electrolyte matrix and each in contact otherwise with a gas phase reagent.
Dans une forme de réalisation plus élaborée, elle peut aussi être utilisée dans un montage monopolaire, en contact avec un électrolyte liquide, auquel cas le procédé de l'inveation est avantageusement complété pour recouvrir l'électrode, du côté de la phase gazeuse, d'une membrane semiporeuse qui forme une barrière imperméable à l'élec¬ trolyte mais perméable au gaz.In a more elaborate embodiment, it can also be used in a monopolar assembly, in contact with a liquid electrolyte, in which case the inveation process is advantageously completed to cover the electrode, on the side of the gas phase, d 'a semiporous membrane which forms a barrier impermeable to electrolyte but permeable to gas.
Suivant une forme de mise en œuvre préférée du procédé, en réalise une telle membrane par pulvérisation de polytétrafluoréthylène en au moins deux étapes successives, une première à partir d'une suspension de polytétrafluoré¬ thylène en microparticules submicroniques, une seconde à partir d'une poudre de granulométrie de l'ordre de 10 à 50 microns,According to a preferred form of implementation of the method, realizes such a membrane by spraying polytetrafluoroethylene in at least two successive stages, a first from a suspension of polytetrafluoro¬ thylene in submicronic microparticles, a second from a granulometry powder of the order of 10 to 50 microns,
On décrira maintenant plus en détail une forme de réalisation particulière de l'invention qui en fera mieux comprendre les caractéristiques essentielles et les avantages, étant entendu toutefois que cette forme de réalisation est choisie à titre d'exemple et qu'elle n'est nullement limitative.A particular embodiment of the invention will now be described in more detail which will make it better understand the essential characteristics and the advantages, it being understood however that this embodiment is chosen by way of example and that it is in no way limiting.
On utilise dans cet exemple, comme support d'élec¬ trode, une mousse de nickel préparée selon un procédé connu qui consiste essentiellement à partir d'une mousse de matière*organique à pores ouverts de porosité au moins égale à 90 % au sein de laquelle on forme un revêtement métallique de nickel comprenant une sous-couche déposée par pulvérisation ou évaporation sous vide et une couche principale déposée par électrolyse.In this example is used as carrier trode élec¬, a nickel foam prepared according to a known process which consists essentially from a foam material * open-pored organic porosity at least equal to 90% in which forms a metallic coating of nickel comprising a sublayer deposited by spraying or evaporation under vacuum and a layer main deposited by electrolysis.
On mélange séparément du polytétrafluoréthylène submicronique en suspension aqueuse (marque déposée Téflon de qualité 30 N présentant une granulometrie de 0,2 micron) avec une poudre de carbone revêtu d'un alliage de platine et de palladium, ou d'un alliage ternaire d'or, platine et palladium. Par laminage, on met la masse active ainsi pré¬ parée sous forme de feuilles minces, souples, où la matière est continue, sans trous. Le polytétrafluoréthylène est sous forme de filaments résultant d'une fibrillation de la poudre.Separately mixing submicronic polytetrafluoroethylene in aqueous suspension (registered trademark Teflon of quality 30 N having a particle size of 0.2 micron) with a carbon powder coated with an alloy of platinum and palladium, or of a ternary alloy of gold, platinum and palladium. By rolling, the active mass is thus prepared in the form of thin, flexible sheets, where the material is continuous, without holes. The polytetrafluoroethylene is in the form of filaments resulting from fibrillation of the powder.
Sur chacune des deux faces opposées du support, on dispose une feuille de masse active ainsi obtenue, et l'on soumet les deux feuilles à une pression mécanique qui les fait pénétrer en film continu dans les pores de la mousse métallique.On each of the two opposite faces of the support, there is a sheet of active mass thus obtained, and the two sheets are subjected to a mechanical pressure which makes them penetrate in continuous film into the pores of the metal foam.
Sur l'une des faces de l'électrode, on réalise ensuite une membrane semiporeuse en polytétrafluoréthylène pur, sans catalyseur. On opère par pulvérisation, en deux étapes, en utilisant d'abord une suspension aqueuse de poudre submicronique (marque déposée Téflon de qualité 30 N), ensuite une poudre sèche présentant une granulo¬ metrie de 20 microns environ (marque déposée Téflon, qualité 702).On one of the faces of the electrode, a semiporous membrane is then produced in pure polytetrafluoroethylene, without catalyst. The operation is carried out by spraying, in two stages, first using an aqueous suspension of submicron powder (registered trademark Teflon of quality 30 N), then a dry powder having a particle size of approximately 20 microns (registered trademark Teflon, quality 702 ).
Naturellement, l'invention n'est en rien limitée par les particularités qui ont été spécifiées dans ce qui précède ou par les détails du mode de réalisation particu¬ lier choisi pour illustrer l'invention. Toutes sortes de variantes peuvent être apportées aux conditions parti- culières de mise en œuvre qui ont été décrites à titre d'exemple sans sortir pour autant du cadre de l'invention. Cette dernière englobe ainsi tous les moyens constituant des équivalents techniques des moyens décrits ainsi que leurs combinaisons. Naturally, the invention is in no way limited by the features which have been specified in the foregoing or by the details of the particular embodiment chosen to illustrate the invention. All kinds of variations can be made to the specific conditions of implementation which have been described by way of example without departing from the scope of the invention. The latter thus includes all the means constituting technical equivalents of the means described as well as their combinations.

Claims

R E V E N D I C A T I O N S
1. Procédé de fabrication d'une électrode de pile à combus¬ tible caractérisé en ce que l'on utilise un support d'élec¬ trode constitué par une mousse métallique et, pour remplir ladite mousse d'une masse active de catalyseur et de liant organique hydrophobe, on met un mélange pulvérulent dudit catalyseur et dudit liant organique sous forme de feuilles laminées continues, on dispose au moins une telle feuille sur au moins une face dudit support, et l'on soumet ladite 0 feuille à une pression sur ledit support pour la faire pénétrer sur la majorité de son épaisseur dans les pores du support.1. A method of manufacturing a fuel cell electrode characterized in that one uses an electrode holder consisting of a metal foam and, to fill said foam with an active mass of catalyst and hydrophobic organic binder, a pulverulent mixture of said catalyst and of said organic binder is put in the form of continuous laminated sheets, at least one such sheet is placed on at least one face of said support, and said 0 sheet is subjected to a pressure on said support to penetrate over most of its thickness into the pores of the support.
2. Procédé selon la revendication 1, caractérisé en ce que ledit liant hydrophobe est du polytétrafluoréthylène. ~2. Method according to claim 1, characterized in that said hydrophobic binder is polytetrafluoroethylene. ~
3. Procédé selon la revendication 2, caractérisé en ce que dans lesdites feuilles le polytétrafluoréthylène est sous forme de filaments résultant de la fibrillation d'une poudre.3. Method according to claim 2, characterized in that in said sheets the polytetrafluoroethylene is in the form of filaments resulting from the fibrillation of a powder.
4. Procédé selon la revendication 1, 2 ou 3» caractérisé en 0 ce que ledit support est une mousse de nickel.4. Method according to claim 1, 2 or 3 " characterized in 0 that said support is a nickel foam.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'on applique deux feuilles de masse active similaires respectivement sur deux faces opposées dudit support. 55. Method according to any one of claims 1 to 4, characterized in that two sheets of similar active mass are applied respectively on two opposite faces of said support. 5
6. Procédé selon la revendication 5, caractérisé en ce que l'on presse chacune desdites feuilles sur ledit support pour remplir la mousse dans toute son épaisseur par inter¬ pénétration d'au moins 50 % , et de préférence de 70 à 90 % de l'épaisseur de chaque feuille. 06. Method according to claim 5, characterized in that each of said sheets is pressed on said support to fill the foam throughout its thickness by inter¬ penetration of at least 50%, and preferably from 70 to 90% of the thickness of each sheet. 0
7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que ledit catalyseur est sous forme d'une poudre à base de platine et/ou de palladium.7. Method according to any one of claims 1 to 6, characterized in that said catalyst is in the form of a powder based on platinum and / or palladium.
8. Procédé selon la revendication 7> caractérisé en ce que ladite poudre est constituée de grains de carbone revêtus 5 d'un alliage de platine et de palladium. 8. Method according to claim 7 > characterized in that said powder consists of carbon grains coated with an alloy of platinum and palladium.
9. Procédé selon la revendication 7, caractérisé en ce que ladite poudre est constituée de grains de carbone revêtus d'un alliage d'or, de platine et de palladium.9. Method according to claim 7, characterized in that said powder consists of carbon grains coated with an alloy of gold, platinum and palladium.
10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que sur une face de l'électrode, on forme une membrane semiporeuse par pulvérisation de poly¬ tétrafluoréthylène en au moins deux étapes succes'sives, une première à partir d'une suspension de polytétra¬ fluoréthylène en microparticules submicroniques, une seconde à partir d'une poudre de granulometrie de l'ordre de 10 à 50 microns. 10. Method according to any one of claims 1 to 9, characterized in that on one face of the electrode, a semiporous membrane is formed by spraying poly¬ tetrafluoroethylene in at least two successive steps, a first from of a suspension of polytetra¬ fluorethylene in submicron microparticles, one second from a powder with a particle size of the order of 10 to 50 microns.
EP90909454A 1989-06-06 1990-06-06 Process for the manufacture of electrodes for fuel cells Withdrawn EP0477246A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8907434 1989-06-06
FR8907434A FR2647968A1 (en) 1989-06-06 1989-06-06 METHOD FOR MANUFACTURING ELECTRODES FROM FUEL CELLS

Publications (1)

Publication Number Publication Date
EP0477246A1 true EP0477246A1 (en) 1992-04-01

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EP90909454A Withdrawn EP0477246A1 (en) 1989-06-06 1990-06-06 Process for the manufacture of electrodes for fuel cells

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EP (1) EP0477246A1 (en)
JP (1) JPH06506314A (en)
CA (1) CA2058938A1 (en)
FR (1) FR2647968A1 (en)
WO (1) WO1990015449A1 (en)

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Publication number Priority date Publication date Assignee Title
FR2715509B1 (en) * 1994-01-27 1996-02-16 Accumulateurs Fixes Secondary electrochemical generator with maintenance-free aqueous electrolyte.
US6368751B1 (en) * 1999-10-08 2002-04-09 Reves, Inc. Electrochemical electrode for fuel cell

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Publication number Priority date Publication date Assignee Title
US3549423A (en) * 1967-06-30 1970-12-22 Gen Electric Method for manufacturing foam type electrode
FR2061501A1 (en) * 1969-02-10 1971-06-25 Inst Francais Du Petrole Hydrophobic electrode coating for fuel cell - s and combustion piles
FR2061527A1 (en) * 1969-04-03 1971-06-25 Inst Francais Du Petrole Fuel cell electrodes with raney nickel catalyst
DE2017702A1 (en) * 1969-04-16 1970-12-03 Dunlop Australia Ltd., Melbourne, Victoria (Australien) electrode
DE2115618A1 (en) * 1971-03-31 1972-10-12 Bosch Gmbh Robert Foils for self-breathing gas diffusion electrodes in electrochemical cells and processes for the production of such foils
US4235748A (en) * 1979-02-28 1980-11-25 Yardney Electric Corporation Method of making improved hydrogenation catalyst
US4354917A (en) * 1980-10-31 1982-10-19 Diamond Shamrock Corporation Gas electrode with asymmetric current distributor
US4370284A (en) * 1980-10-31 1983-01-25 Diamond Shamrock Corporation Non-bleeding electrode
JPS6017863A (en) * 1983-07-08 1985-01-29 Matsushita Electric Ind Co Ltd Manufacture of gas diffusion catalyst electrode
DE3342969A1 (en) * 1983-11-28 1985-06-05 Varta Batterie Ag, 3000 Hannover POROESE GAS ELECTRODE
JPS6122570A (en) * 1984-07-09 1986-01-31 Toshiba Corp Manufacture of air electrode

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Title
See references of WO9015449A1 *

Also Published As

Publication number Publication date
FR2647968A1 (en) 1990-12-07
CA2058938A1 (en) 1990-12-07
JPH06506314A (en) 1994-07-14
WO1990015449A1 (en) 1990-12-13

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