WO2009080920A2 - Electrode comprising poly(3,4-ethylene dioxythiophene)/polystyrene sulfonate - Google Patents

Electrode comprising poly(3,4-ethylene dioxythiophene)/polystyrene sulfonate Download PDF

Info

Publication number
WO2009080920A2
WO2009080920A2 PCT/FR2008/001417 FR2008001417W WO2009080920A2 WO 2009080920 A2 WO2009080920 A2 WO 2009080920A2 FR 2008001417 W FR2008001417 W FR 2008001417W WO 2009080920 A2 WO2009080920 A2 WO 2009080920A2
Authority
WO
WIPO (PCT)
Prior art keywords
poly
fuel cell
catalyst
polymer
catalytic
Prior art date
Application number
PCT/FR2008/001417
Other languages
French (fr)
Other versions
WO2009080920A3 (en
Inventor
Antoine Latour
Sylvain Nizou
Original Assignee
Commissariat A L'energie Atomique
St Microelectronics (Tours) Sas
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 Commissariat A L'energie Atomique, St Microelectronics (Tours) Sas filed Critical Commissariat A L'energie Atomique
Publication of WO2009080920A2 publication Critical patent/WO2009080920A2/en
Publication of WO2009080920A3 publication Critical patent/WO2009080920A3/en

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
    • H01M4/92—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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • 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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • 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 invention relates to the use of a proton and electronically conductive polymer, hereinafter referred to as a poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) mixed polymer for the manufacture of a catalytic ink, as well as the catalytic ink itself. even.
  • It also relates to a fuel cell electrode, a fuel cell membrane-electrode assembly and a fuel cell comprising a poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) mixed polymer.
  • Fuel cells are energy conversion devices that are currently highly studied, particularly to supply energy to internal combustion engines, replacing the energy sources currently used.
  • One type of fuel cell is the proton exchange membrane fuel cell.
  • the electrodes are separated by an electrically insulating but conductive medium called electrolyte, this electrolyte being a solid. More particularly, this membrane is a polymer such as National ® or Hyflon ®.
  • This type of battery requires the presence of a catalyst on the face of the electrodes in contact with the electrolyte which, as recalled, is constituted by the proton exchange membrane.
  • This face of the electrodes on which the catalysts are present will be called hereinafter "active face”.
  • the most effective catalyst for most reactions and fuels is platinum.
  • the active faces of the carbon electrodes are impregnated.
  • the impregnation of the supported catalyst is not uniform, with areas not completely impregnated and other areas where the polymeric solid electrolyte material extends very deep into the electrode and thus prevents diffusion of the gas through the electrode.
  • hydrophobic binder blocks the access of protons and oxygen to the catalytic site of the cathode.
  • the most widespread method currently for uniformly and efficiently distributing the catalyst on the useful face of the electrode is to deposit the catalyst which is included in what is called a catalytic ink.
  • This catalytic ink comprises, in addition to the supported catalyst, suspended materials which are volatile or decomposable to form a film on the useful face of the electrode.
  • These methods include flexography, heliography, screen printing, spray coating or ink jet deposition.
  • the conventional formulation of the catalytic inks of fuel cells comprises the catalyst as carbon nanoparticles dispersed on that provides electronic conductivity, a carrier liquid, generally water, and a proton conducting polymer in solution such as Nafion ® or 'Hyflon ® .
  • this type of formulation does not take into account the requirements imposed by the printheads used in paper printing processes.
  • the formulation of the catalytic inks for fuel cells must be adapted to the ejection heads used.
  • the first solution poses problems of ejection of such an ink which has too much solids.
  • the second solution leads to a decrease in the number of triple points.
  • the triple point cited here is not the triple point of physicists, but the point where gaseous oxygen, electrons and protons must be brought into contact with the platinum catalyst in the case of the cathode.
  • the catalytic sites, as well as the carbon particles which are the electronic conductor are isolated from each other by the polymer, thus reducing the number of triple points and the efficiency of the electrode.
  • the invention proposes a catalytic ink whose formulation is suitable for use with deposition methods resulting from the printing of paper such as coating, inkjet, flexography, heliography, screen printing and vapor deposition, by adapting the viscosity of this ink to the ejection head used, without adding any species likely to poison the catalysts or degrade the performance of the fuel cell while maintaining the proton and electronic conductivity of the proton exchange membrane fuel cell electrodes.
  • an expensive polymer such as Nafion ® or Hyflon ® .
  • the invention proposes the use of a mixed polymer poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) for the manufacture of a catalytic ink.
  • Another object of the invention is a catalytic ink of the type comprising a catalyst and a polymer, characterized in that said polymer is a mixed polymer poly (3,4-ethylenedioxythiophene) poly (styrenesulphonate).
  • the catalytic ink of the invention comprises between 0.5 and 20% by weight, preferably 5% by weight of said mixed polymer.
  • the catalyst / mixed polymer mass ratio of the catalytic ink of the invention is between 0.01 and 1 inclusive.
  • it is 0.1.
  • Yet another object of the invention is a fuel cell electrode comprising a poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) mixed polymer.
  • Still another object of the invention is a fuel cell membrane-electrolyte assembly comprising a poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) mixed polymer.
  • the invention also provides a fuel cell comprising a poly (y-3,4-ethylenedioxythiophene) poly (styrenesulfonate) mixed polymer.
  • the invention still proposes the use of the catalytic ink of the invention for the manufacture of a fuel cell electrode.
  • Another object of the invention is the use of the catalytic ink according to the invention for the manufacture of an electrode-membrane assembly of a fuel cell.
  • Yet another object of the invention is the use of the catalytic ink according to the invention for the manufacture of a fuel cell.
  • Still another object of the invention is a method of depositing a catalytic ink according to the invention which is produced by ink jet.
  • a first object of the invention is the use of a mixed polymer poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate), commonly called PEDOT-PSS, for the manufacture of a catalytic ink.
  • PEDOT-PSS a mixed polymer poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate), commonly called PEDOT-PSS
  • PEDOT-PSS is a polymeric mixture of two ionomers.
  • One component of this mixture is sodium polystyrene sulfonate which is a sulfonated polystyrene. Some of the sulfonyl groups are deprotonated and carry a negative charge.
  • the other component, poly (3,4-ethylenedioxythiophene) or PEDOT, is a conjugated polymer that carries positive charges based on polythiophene.
  • PEDOT-PSS is generally used as a conductive polymer.
  • the sulfonate groups are the proton conductors and the delocalized electrons are the electronic conductors.
  • this polymer has both electronic and protonic conduction properties.
  • this polymer according to the invention it is therefore possible to vary the viscosity of conventional catalytic inks and it is no longer necessary to add another proton polymer, such as Nafion ® or Hyflon ® used in the prior art, which are expensive polymers.
  • the excess of polymer in the catalytic ink does not isolate the catalytic sites because there is always a good mixed conduction provided by the sulfonate groups and the delocalized electrons of this polymer.
  • the invention also relates to a catalytic ink comprising, in addition to the catalyst, generally platinum, a mixed polymer PEDOT-PSS.
  • Table 1 summarizes the viscosity desired for printing inks according to the printing process used.
  • this weight ratio of PEDOT-PSS polymer / catalyst mass is between 1 and 10.
  • the ratio by weight of polymer / mixed catalyst PEDOT-PSS of the catalytic ink of the invention is 10 because it allows to obtain a viscosity of the ink which makes it possible to apply it by ink jet printing.
  • the formulation of the catalytic inks of the invention will comprise between 0.5 and 20% by weight, preferably 5% by weight, of PEDOT-PSS polymer, according to the printing process that it is desired to apply, in order to to adjust the viscosity.
  • the catalytic ink will preferably comprise between 5% by weight of PEDOT-PSS polymer, based on the total mass of the ink, to obtain a viscosity of 10 mPa.s necessary for the ejection in the ink jet process.
  • the catalytic ink of the invention will comprise in addition to the catalyst, generally platinum in the form of nanoparticles dispersed on carbon, and the PEDOT-PSS polymer, a carrier liquid, such as water.
  • fuel cell electrodes can be produced by applying the catalyst to the electrode by a deposition method generally used for printing and, more particularly, by the jet method. 'ink.
  • the invention also relates to the use of the catalytic ink of the invention for the manufacture of fuel cell electrodes, for the manufacture of a fuel cell membrane-electrolyte assembly and for the manufacture of a fuel cell.
  • catalytic ink About 50 ml of catalytic ink are prepared in the following manner: Carbon-dispersed catalyst nanoparticles are suspended in an aqueous solvent (between 0.5 and 10% by mass of particles).
  • the mixed polymer is then added in order to adapt the viscosity of the solution (5% by weight, in order to reach a viscosity of the order of 10 mPa.s).
  • the ink is then placed in an ultrasonic bath and stirred on a magnetic stirrer.
  • the solution is placed in the tank of the print head; a nozzle of 60 microns in diameter allows ejection of the drops on the substrate.
  • the voltage amplitude applied to the piezoelectric (of the ink jet head) is 60 V.

Abstract

The invention relates to the use of a poly(3,4-ethylene dioxythiophene)/polystyrene sulfonate mixed polymer for manufacturing a catalytic ink and to the catalytic ink itself. The invention also relates to a fuel cell electrode, to a fuel cell electrode-membrane assembly and to a fuel cell comprising a poly(3,4-ethylene dioxythiophene)/polystyrene sulfonate mixed polymer. The invention is applicable in particular in the field of supplying energy for internal combustion engines.

Description

ELECTRODE COMPRENANT DU POLY(3,4-ETHYLENEDIOXYTHIOPHENE) POLY(STYRENESULFONATE) ELECTRODE COMPRISING POLY (3,4-ETHYLENEDIOXYTHIOPHENE) POLY (STYRENESULFONATE)
L'invention concerne l'utilisation d'un polymère à conduction protonique et électronique appelé par la suite polymère mixte poly(3,4- éthylènedioxythiophène) poly(styrènesulfonate) pour la fabrication d'une encre catalytique ainsi que l'encre catalytique elle-même.The invention relates to the use of a proton and electronically conductive polymer, hereinafter referred to as a poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) mixed polymer for the manufacture of a catalytic ink, as well as the catalytic ink itself. even.
Elle concerne également une électrode de pile à combustible, un assemblage électrodes-membrane de pile à combustible et une pile à combustible comprenant un polymère mixte poly(3,4-éthylènedioxythiophène) poly(styrènesulfonate).It also relates to a fuel cell electrode, a fuel cell membrane-electrode assembly and a fuel cell comprising a poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) mixed polymer.
Les piles à combustibles sont des dispositifs de conversion d'énergie qui sont actuellement très étudiés, en particulier pour alimenter en énergie les moteurs à combustion interne, en remplacement des sources d'énergie actuellement utilisées.Fuel cells are energy conversion devices that are currently highly studied, particularly to supply energy to internal combustion engines, replacing the energy sources currently used.
Un type de piles à combustible est à la pile à combustible à membrane échangeuse de protons.One type of fuel cell is the proton exchange membrane fuel cell.
Dans ce type de piles, les électrodes (anode et cathode) sont séparées par un milieu isolant électronique mais conducteur appelé électrolyte, cet électrolyte étant un solide. Plus particulièrement cette membrane est un polymère tel que le Nation® ou l'Hyflon®.In this type of battery, the electrodes (anode and cathode) are separated by an electrically insulating but conductive medium called electrolyte, this electrolyte being a solid. More particularly, this membrane is a polymer such as Nation ® or Hyflon ®.
Ce type de piles nécessite la présence d'un catalyseur sur la face des électrodes en contact avec l'électrolyte qui, on le rappelle, est constitué par la membrane échangeuse de protons. Cette face des électrodes sur laquelle les catalyseurs sont présents sera appelée ci-après "face active".This type of battery requires the presence of a catalyst on the face of the electrodes in contact with the electrolyte which, as recalled, is constituted by the proton exchange membrane. This face of the electrodes on which the catalysts are present will be called hereinafter "active face".
En tant que catalyseur, le catalyseur le plus efficace pour la plupart des réactions et des combustibles est le platine.As the catalyst, the most effective catalyst for most reactions and fuels is platinum.
Ces catalyseurs ont d'abord été incorporés par pressage à chaud des électrodes directement sur la surface de la membrane d'électrolyte polymère solide. Cependant, la grande quantité de platine utilisée dans ce cas rendait les piles à combustible ainsi obtenues non compétitives avec d'autres sources d'énergie.These catalysts were first incorporated by hot pressing the electrodes directly onto the surface of the solid polymer electrolyte membrane. However, the large amount of platinum used in this case made the resulting fuel cells uncompetitive with other energy sources.
On a alors proposé de réduire la charge en platine requise en utilisant un catalyseur platine supporté sur des particules ou des tissus ou des substrats à base de carbone, liés à l'électrode par un composant hydrophobe tel que le polytétrafluoroéthylène.It was then proposed to reduce the required platinum loading by using a platinum catalyst supported on carbon-based particles or fabrics or substrates bound to the electrode by a hydrophobic component such as polytetrafluoroethylene.
Dans ce cas, les faces actives des électrodes de carbone sont imprégnées. Cependant, par ce procédé, l'imprégnation du catalyseur supporté n'est pas uniforme, avec des zones non complètement imprégnées et d'autres zones où le matériau électrolyte solide polymère s'étend très profondément dans l'électrode et ainsi empêche la diffusion du gaz à travers l'électrode.In this case, the active faces of the carbon electrodes are impregnated. However, by this process, the impregnation of the supported catalyst is not uniform, with areas not completely impregnated and other areas where the polymeric solid electrolyte material extends very deep into the electrode and thus prevents diffusion of the gas through the electrode.
De plus, le liant hydrophobe bloque l'accès des protons et de l'oxygène au site catalytique de la cathode.In addition, the hydrophobic binder blocks the access of protons and oxygen to the catalytic site of the cathode.
Ainsi, la méthode la plus répandue actuellement pour répartir de façon uniforme et efficace le catalyseur sur la face utile de l'électrode est de déposer le catalyseur qui est inclus dans ce qu'on appelle une encre catalytique.Thus, the most widespread method currently for uniformly and efficiently distributing the catalyst on the useful face of the electrode is to deposit the catalyst which is included in what is called a catalytic ink.
Cette encre catalytique comprend, outre le catalyseur supporté, des matériaux en suspension qui sont volatiles ou décomposables pour former un film sur la face utile de l'électrode.This catalytic ink comprises, in addition to the supported catalyst, suspended materials which are volatile or decomposable to form a film on the useful face of the electrode.
Différentes méthodes ont été utilisées, dont la méthode de dépôt par plasma.Different methods were used, including the plasma deposition method.
On connaît par ailleurs, des procédés de dépôt d'encre dans le domaine de l'impression du papier.In addition, there are known methods of depositing ink in the field of paper printing.
Parmi ces procédés, on peut citer la flexographie, l'héliographie, la sérigraphie, le revêtement par vaporisation ou encore le dépôt par jet d'encre.These methods include flexography, heliography, screen printing, spray coating or ink jet deposition.
La fiabilité de ces procédés repose sur les formulations précises des encres qu'il est nécessaire d'adapter au procédé choisi. L'un des facteurs clefs pour la formulation d'une encre adaptée pour un dépôt par un procédé d'impression de papier est sa viscosité. Pour obtenir la viscosité voulue, il est indispensable de choisir le liquide porteur et les additifs de façon à atteindre les valeurs voulues.The reliability of these processes is based on the precise formulations of the inks that must be adapted to the chosen process. One of the key factors in formulating an ink suitable for deposition by a paper printing process is its viscosity. To obtain the desired viscosity, it is essential to choose the carrier liquid and the additives in order to reach the desired values.
Des composés comme l'éthylène glycol ou la glycérine sont généralement utilisés dans les encres d'imprimerie pour modifier leur viscosité. La formulation classique des encres catalytiques de piles à combustible comprend le catalyseur sous forme de nanoparticules dispersées sur carbone qui assure la conductibilité électronique, un liquide porteur, généralement de l'eau, et un polymère conducteur protonique en solution tel que le Nafion® ou l'Hyflon®. Cependant, ce type de formulation ne tient pas compte des exigences imposées par les têtes d'impression utilisées dans les procédés d'impression du papier.Compounds such as ethylene glycol or glycerine are generally used in printing inks to modify their viscosity. The conventional formulation of the catalytic inks of fuel cells comprises the catalyst as carbon nanoparticles dispersed on that provides electronic conductivity, a carrier liquid, generally water, and a proton conducting polymer in solution such as Nafion ® or 'Hyflon ® . However, this type of formulation does not take into account the requirements imposed by the printheads used in paper printing processes.
Ainsi, pour pouvoir utiliser les procédés d'impression de l'imprimerie pour la fabrication d'une pile à combustible, la formulation des encres catalytiques pour piles à combustible doit être adaptée aux têtes d'éjection utilisées.Thus, in order to be able to use the printing processes of the printing press for the manufacture of a fuel cell, the formulation of the catalytic inks for fuel cells must be adapted to the ejection heads used.
Par conséquent, à la formulation classique des encres catalytiques de piles à combustible citée ci-dessus, il est nécessaire d'ajouter, à la glycérine, un composé permettant d'abaisser la tension de surface, par exemple l'isopropanol.Therefore, in the conventional formulation of the fuel cell catalytic inks mentioned above, it is necessary to add to the glycerine a compound for lowering the surface tension, for example isopropanol.
Or, ces composés permettant d'augmenter la viscosité de l'encre possèdent une température d'ébullition élevée, de l'ordre de 180 à 2000C, peu compatible avec les températures de recuit utilisées dans la technologie de fabrication des piles à combustible : la dégradation du polymère conducteur protonique doit être effectuée à température trop élevée. Ils sont donc difficiles à évaporer après dépôt de l'encre et restent présents dans les électrodes.However, these compounds making it possible to increase the viscosity of the ink have a high boiling point, of the order of 180 to 200 ° C., which is not very compatible with the annealing temperatures used in fuel cell manufacturing technology. : the degradation of the proton conducting polymer must be carried out at too high a temperature. They are therefore difficult to evaporate after deposition of the ink and remain present in the electrodes.
La présence de ces composés dans les électrodesThe presence of these compounds in the electrodes
(essentiellement la cathode) entraîne l'existence d'un potentiel mixte compris entre le potentiel de réduction de l'oxygène, à la cathode, et le potentiel d'oxydation du composé restant. Il en résulte une diminution de la différence de potentiel et donc de la tension de la pile et ainsi une baisse des performances de la pile. De plus, ces composés sont susceptibles d'engendrer la formation de poisons, bloquant les catalyseurs et réduisant ainsi l'activité des électrodes.(essentially the cathode) causes the existence of a mixed potential between the oxygen reduction potential at the cathode and the oxidation potential of the remaining compound. This results in a decrease in the potential difference and therefore the battery voltage and thus a drop in the performance of the battery. In addition, these compounds are likely to cause the formation of poisons, blocking the catalysts and thus reducing the activity of the electrodes.
Afin d'obtenir une viscosité suffisamment élevée de l'encre catalytique, pour pouvoir l'appliquer par des procédés issus de l'impression du papier, il peut sembler possible d'augmenter la teneur en particules du catalyseur ou la concentration de la solution de polymère conducteur protonique.In order to obtain a sufficiently high viscosity of the catalytic ink, in order to be able to apply it by processes resulting from the printing of the paper, it may seem possible to increase the particle content of the catalyst or the concentration of the catalyst solution. proton conductive polymer.
Cependant, la première solution pose des problèmes d'éjection d'une telle encre qui présente un extrait sec trop important. La seconde solution entraîne une diminution du nombre de points triples. Le point triple cité ici n'est pas le point triple des physiciens, mais le point où l'oxygène gazeux, les électrons et les protons doivent être mis en contact sur le catalyseur de platine, dans le cas de la cathode.However, the first solution poses problems of ejection of such an ink which has too much solids. The second solution leads to a decrease in the number of triple points. The triple point cited here is not the triple point of physicists, but the point where gaseous oxygen, electrons and protons must be brought into contact with the platinum catalyst in the case of the cathode.
Ainsi, dans le cas de l'utilisation d'un excès de polymère, les sites catalytiques, ainsi que les particules de carbone qui sont le conducteur électronique, sont isolés l'un de l'autre par le polymère, réduisant ainsi le nombre de points triples et l'efficacité de l'électrode.Thus, in the case of the use of an excess of polymer, the catalytic sites, as well as the carbon particles which are the electronic conductor, are isolated from each other by the polymer, thus reducing the number of triple points and the efficiency of the electrode.
En effet il est nécessaire de conserver un rapport catalyseur/polymère conducteur protonique optimal.Indeed it is necessary to maintain an optimal catalyst / proton conductive polymer ratio.
Ainsi, Song & al. dans Optimal composition of polymer Elecrolyte fuel cell électrodes determined by the AC impédance method , Journal of Power Sources 94 (2001) 78-84, enseignent de conserver un rapport masse de Pt sur masse de polymère protonique en général de 0,5.Thus, Song & al. in Optimal composition of polymer Elecrolyte fuel cell electrodes determined by the AC impedance method, Journal of Power Sources 94 (2001) 78-84, teach to maintain a mass ratio of Pt to proton polymer mass in general of 0.5.
Afin de résoudre les problèmes de l'art antérieur, l'invention propose une encre catalytique dont la formulation est adaptée pour une utilisation avec des méthodes de dépôt issues de l'impression du papier telles que l'enduction, le jet d'encre, la flexographie, l'héliographie, la sérigraphie et le dépôt par vaporisation, en adaptant la viscosité de cette encre à la tête d'éjection utilisée, sans pour autant ajouter d'espèces susceptibles d'empoisonner les catalyseurs ou de dégrader les performances de la pile à combustible tout en conservant la conductivité protonique et électronique des électrodes de piles à combustible à membrane échangeuse de protons. De plus, avec l'encre catalytique de l'invention, il n'est plus nécessaire d'utiliser un polymère coûteux tel que le Nafion®ou l'Hyflon®.In order to solve the problems of the prior art, the invention proposes a catalytic ink whose formulation is suitable for use with deposition methods resulting from the printing of paper such as coating, inkjet, flexography, heliography, screen printing and vapor deposition, by adapting the viscosity of this ink to the ejection head used, without adding any species likely to poison the catalysts or degrade the performance of the fuel cell while maintaining the proton and electronic conductivity of the proton exchange membrane fuel cell electrodes. In addition, with the catalytic ink of the invention, it is no longer necessary to use an expensive polymer such as Nafion ® or Hyflon ® .
A cet effet, l'invention propose l'utilisation d'un polymère mixte poly(3,4-éthylènedioxythiophène) poly(styrènesulfonate) pour la fabrication d'une encre catalytique.For this purpose, the invention proposes the use of a mixed polymer poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) for the manufacture of a catalytic ink.
Un autre objet de l'invention est une encre catalytique du type comprenant un catalyseur et un polymère, caractérisée en ce que ledit polymère est un polymère mixte poly(3,4-éthylènedioxythiophène) poly(styrènesulfonate).Another object of the invention is a catalytic ink of the type comprising a catalyst and a polymer, characterized in that said polymer is a mixed polymer poly (3,4-ethylenedioxythiophene) poly (styrenesulphonate).
De préférence, l'encre catalytique de l'invention comprend entre 0,5 et 20 % en masse inclus, de préférence 5 % en masse dudit polymère mixte.Preferably, the catalytic ink of the invention comprises between 0.5 and 20% by weight, preferably 5% by weight of said mixed polymer.
De préférence le rapport en masse catalyseur/polymère mixte de l'encre catalytique de l'invention est compris entre 0,01 et 1 inclus.Preferably, the catalyst / mixed polymer mass ratio of the catalytic ink of the invention is between 0.01 and 1 inclusive.
De préférence, il est de 0,1.Preferably, it is 0.1.
Encore un autre objet de l'invention est une électrode de pile à combustible comprenant un polymère mixte poly(3,4-éthylènedioxythiophène) poly(styrènesulfonate).Yet another object of the invention is a fuel cell electrode comprising a poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) mixed polymer.
Toujours un autre objet de l'invention est un assemblage électrodes-membrane de pile à combustible comprenant un polymère mixte poly(3,4-éthylènedioxythiophène) poly(styrènesulfonate). L'invention propose également une pile à combustible comprenant un polymère mixte po!y(3,4-éthylènedioxythiophène) poly(styrènesulfonate).Still another object of the invention is a fuel cell membrane-electrolyte assembly comprising a poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) mixed polymer. The invention also provides a fuel cell comprising a poly (y-3,4-ethylenedioxythiophene) poly (styrenesulfonate) mixed polymer.
Mais, l'invention propose encore l'utilisation de l'encre catalytique de l'invention pour la fabrication d'une électrode pile à combustible.However, the invention still proposes the use of the catalytic ink of the invention for the manufacture of a fuel cell electrode.
Un autre objet de l'invention est l'utilisation de l'encre catalytique selon l'invention pour la fabrication d'un assemblage électrodes-membrane d'une pile à combustible.Another object of the invention is the use of the catalytic ink according to the invention for the manufacture of an electrode-membrane assembly of a fuel cell.
Encore un autre objet de l'invention est l'utilisation de l'encre catalytique selon l'invention pour la fabrication d'une pile à combustible.Yet another object of the invention is the use of the catalytic ink according to the invention for the manufacture of a fuel cell.
Toujours un autre objet de l'invention est un procédé de dépôt d'une encre catalytique selon l'invention qui est réalisé par jet d'encre. L'invention sera mieux comprise et d'autres caractéristiques et avantages de celle-ci apparaîtront plus clairement à la lecture de la description explicative qui suit.Still another object of the invention is a method of depositing a catalytic ink according to the invention which is produced by ink jet. The invention will be better understood and other features and advantages thereof will appear more clearly on reading the explanatory description which follows.
Un premier objet de l'invention est l'utilisation d'un polymère mixte poly(3,4-éthylènedioxythiophène) poly(styrènesulfonate), appelé couramment PEDOT-PSS, pour la fabrication d'une encre catalytique.A first object of the invention is the use of a mixed polymer poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate), commonly called PEDOT-PSS, for the manufacture of a catalytic ink.
Le PEDOT-PSS est un mélange polymérique de deux ionomères. Un composant de ce mélange est constitué de sodium polystyrènesulfonate qui est un polystyrène sulfonaté. Une partie des groupes sulfoniles sont déprotonés et portent une charge négative. L'autre composant, le poly(3,4- éthylènedioxythiophène) ou PEDOT, est un polymère conjugué qui porte des charges positives à base de polythiophène.PEDOT-PSS is a polymeric mixture of two ionomers. One component of this mixture is sodium polystyrene sulfonate which is a sulfonated polystyrene. Some of the sulfonyl groups are deprotonated and carry a negative charge. The other component, poly (3,4-ethylenedioxythiophene) or PEDOT, is a conjugated polymer that carries positive charges based on polythiophene.
Les deux macromolécules chargées forment ensemble un sel macromoléculaire. Le PEDOT-PSS est généralement utilisé en tant que polymère conducteur. Ainsi, dans ce polymère mixte, les groupements sulfonates sont les conducteurs protoniques et les électrons délocalisés sont les conducteurs électroniques. Ce qui fait que ce polymère possède des propriétés de conduction à la fois électronique et protonique.The two charged macromolecules together form a macromolecular salt. PEDOT-PSS is generally used as a conductive polymer. Thus, in this mixed polymer, the sulfonate groups are the proton conductors and the delocalized electrons are the electronic conductors. As a result, this polymer has both electronic and protonic conduction properties.
Grâce à l'utilisation de ce polymère, selon l'invention, on peut donc faire varier la viscosité des encres catalytiques classiques et il n'est plus nécessaire d'ajouter un autre polymère protonique, tel que le Nafion® ou l'Hyflon® utilisés dans l'art antérieur, qui sont des polymères onéreux.Through the use of this polymer according to the invention, it is therefore possible to vary the viscosity of conventional catalytic inks and it is no longer necessary to add another proton polymer, such as Nafion ® or Hyflon ® used in the prior art, which are expensive polymers.
De plus, l'excès de polymère dans l'encre catalytique n'isole pas les sites catalytiques car il existe toujours une bonne conduction mixte assurée par les groupements sulfonates et les électrons délocalisés de ce polymère.In addition, the excess of polymer in the catalytic ink does not isolate the catalytic sites because there is always a good mixed conduction provided by the sulfonate groups and the delocalized electrons of this polymer.
Il n'est pas non plus nécessaire d'ajouter des composés organiques tel que les glycols pour augmenter la viscosité de l'encre et pour l'adapter au procédé d'impression.It is also not necessary to add organic compounds such as glycols to increase the viscosity of the ink and to adapt it to the printing process.
De ce fait, il n'existe pas d'empoisonnement des sites catalytiques par la présence de composés organiques résiduels après séchage, et il n'existe pas de potentiel mixte entraînant une diminution de la différence de potentiel. Dès lors, l'invention concerne également une encre catalytique comprenant, outre le catalyseur, généralement le platine, un polymère mixte PEDOT-PSS.As a result, there is no poisoning of the catalytic sites by the presence of residual organic compounds after drying, and there is no mixed potential leading to a decrease in the potential difference. Therefore, the invention also relates to a catalytic ink comprising, in addition to the catalyst, generally platinum, a mixed polymer PEDOT-PSS.
Le tableau 1 ci-dessous récapitule la viscosité voulue pour les encres d'imprimerie en fonction du procédé d'imprimerie utilisé.Table 1 below summarizes the viscosity desired for printing inks according to the printing process used.
Figure imgf000008_0001
Figure imgf000008_0001
Tableau 1Table 1
II est connu qu'un rapport optimal entre la masse de catalyseur et la masse de polymère conducteur protonique dans la formulation d'encre existe. C'est ainsi que, comme déjà dit, Song et al. dans Optimal composition of polymer electrolyte fuel cell électrodes determined by the AC impédance method Journal of Power Sources, Vol. 94, 2001 , pages 78-84, enseignent de conserver un rapport masse de Pt sur masse de polymère protonique de 0,5, c'est-à-dire, un rapport masse de polymère protonique sur masse de catalyseur de 2.It is known that an optimum ratio of the catalyst mass to the proton conductive polymer mass in the ink formulation exists. Thus, as already said, Song et al. in Optimal composition of polymer electrolyte fuel cell electrodes determined by the AC impedance method Journal of Power Sources, Vol. 94, 2001, pages 78-84, teach to maintain a Pt mass to proton mass ratio of 0.5, i.e., a mass ratio of proton polymer to catalyst mass of 2.
Dans l'invention, ce rapport masse de polymère PEDOT-PSS / masse de catalyseur est compris entre 1 et 10.In the invention, this weight ratio of PEDOT-PSS polymer / catalyst mass is between 1 and 10.
De préférence, il est supérieur à 2 pour non seulement obtenir la viscosité voulue de l'encre catalytique de l'invention pour pouvoir utiliser le procédé d'impression que l'on souhaite appliquer, mais également pour améliorer la conduction électrique du film formé à partir de cette encre catalytique. En effet, le polymère mixte PEDOT-PSS étant lui-même conducteur, n'isole pas les sites catalytiques du conducteur et n'entraîne pas de diminution du nombre de points triples. Le plus préférablement, le rapport en masse polymère / catalyseur mixte PEDOT-PSS de l'encre catalytique de l'invention est de 10 car il permet d'obtenir une viscosité de l'encre qui permet de l'appliquer par impression par jet d'encre.Preferably, it is greater than 2 to not only obtain the desired viscosity of the catalytic ink of the invention in order to be able to use the printing process that it is desired to apply, but also to improve the electrical conduction of the film formed in from this catalytic ink. Indeed, the mixed polymer PEDOT-PSS itself being conductive, does not isolate the catalytic sites of the driver and does not lead to a decrease in the number of triple points. Most preferably, the ratio by weight of polymer / mixed catalyst PEDOT-PSS of the catalytic ink of the invention is 10 because it allows to obtain a viscosity of the ink which makes it possible to apply it by ink jet printing.
Ainsi, la formulation des encres catalytiques de l'invention comprendra entre 0,5 et 20 % en masse, de préférence 5 % en masse, de polymère PEDOT-PSS, selon le procédé d'impression que l'on souhaite appliquer, afin d'adapter la viscosité.Thus, the formulation of the catalytic inks of the invention will comprise between 0.5 and 20% by weight, preferably 5% by weight, of PEDOT-PSS polymer, according to the printing process that it is desired to apply, in order to to adjust the viscosity.
Pour le procédé jet d'encre, l'encre catalytique comprendra de préférence entre 5 % en masse de polymère PEDOT-PSS, par rapport à la masse totale de l'encre, pour obtenir une viscosité de 10 mPa.s nécessaire pour l'éjection dans le procédé à jet d'encre.For the ink-jet process, the catalytic ink will preferably comprise between 5% by weight of PEDOT-PSS polymer, based on the total mass of the ink, to obtain a viscosity of 10 mPa.s necessary for the ejection in the ink jet process.
Bien entendu, l'encre catalytique de l'invention comprendra outre le catalyseur, généralement du platine sous forme de nanoparticules dispersées sur du carbone, et le polymère PEDOT-PSS, un liquide porteur, comme l'eau.Of course, the catalytic ink of the invention will comprise in addition to the catalyst, generally platinum in the form of nanoparticles dispersed on carbon, and the PEDOT-PSS polymer, a carrier liquid, such as water.
Grâce à l'encre catalytique de l'invention, on peut fabriquer des électrodes pour piles à combustible en appliquant le catalyseur sur l'électrode par une méthode de dépôt généralement utilisée pour l'impression et, plus particulièrement, par la méthode du jet d'encre.Thanks to the catalytic ink of the invention, fuel cell electrodes can be produced by applying the catalyst to the electrode by a deposition method generally used for printing and, more particularly, by the jet method. 'ink.
On peut également, grâce à l'encre catalytique de l'invention, fabriquer un assemblage électrodes-membrane pour pile à combustible ainsi qu'une pile à combustible elle-même.It is also possible, thanks to the catalytic ink of the invention, to manufacture an electrode-membrane assembly for a fuel cell as well as a fuel cell itself.
Ces électrodes, cet assemblage électrodes-membrane et cette pile à combustible sont également des objets de l'invention.These electrodes, this electrode-membrane assembly and this fuel cell are also objects of the invention.
Autrement dit, l'invention concerne également l'utilisation de l'encre catalytique de l'invention pour la fabrication d'électrodes de piles à combustible, pour la fabrication d'un assemblage électrodes-membrane de pile à combustible et pour la fabrication d'une pile à combustible.In other words, the invention also relates to the use of the catalytic ink of the invention for the manufacture of fuel cell electrodes, for the manufacture of a fuel cell membrane-electrolyte assembly and for the manufacture of a fuel cell.
Ces utilisations font également partie de l'invention.These uses are also part of the invention.
Afin de mieux faire comprendre l'invention, on va en décrire maintenant à titre purement illustratif et non limitatif un exemple de mise en œuvre. Exemple 1 : Fabrication d'une encre catalytique selon l'invention pour une application par la méthode d'impression par jet d'encre.To better understand the invention, will now be described by way of illustrative and not limiting an example of implementation. EXAMPLE 1 Manufacture of a Catalytic Ink According to the Invention for Application by the Inkjet Printing Method
Environ 50 ml_ d'encre catalytique sont préparés de la façon suivante: - Les nanoparticules de catalyseur dispersées sur carbone sont mises en suspension dans un solvant aqueux (entre 0,5 et 10 % en masse de particules).About 50 ml of catalytic ink are prepared in the following manner: Carbon-dispersed catalyst nanoparticles are suspended in an aqueous solvent (between 0.5 and 10% by mass of particles).
On ajoute ensuite le polymère mixte afin d'adapter la viscosité de la solution (5 % en masse, afin d'atteindre une viscosité de l'ordre de 10 mPa.s).The mixed polymer is then added in order to adapt the viscosity of the solution (5% by weight, in order to reach a viscosity of the order of 10 mPa.s).
L'encre est ensuite placée dans un bain à ultrasons, puis agitée sur agitateur magnétique.The ink is then placed in an ultrasonic bath and stirred on a magnetic stirrer.
Un équipement jet d'encre (Altadrop de chez AltatechInkjet equipment (Altadrop from Altatech
(Montbonot (38)) est ensuite utilisé pour l'éjection de l'encre. La solution est placée dans le réservoir de la tête d'impression ; une buse de 60 μm de diamètre permet l'éjection des gouttes sur le substrat. L'amplitude de tension appliquée au piézoélectrique (de la tête jet d'encre) est de 60 V. (Montbonot (38)) is then used for the ejection of the ink. The solution is placed in the tank of the print head; a nozzle of 60 microns in diameter allows ejection of the drops on the substrate. The voltage amplitude applied to the piezoelectric (of the ink jet head) is 60 V.

Claims

REVENDICATIONS
1. Encre catalytique comprenant un catalyseur et un polymère mixte de poly(3,4-éthylènedioxythiophène / polystyrènesulfonate caractérisée en ce que le rapport en masse dudit polymère mixte / catalyseur est supérieur à 2.A catalytic ink comprising a catalyst and a mixed polymer of poly (3,4-ethylenedioxythiophene / polystyrenesulfonate characterized in that the mass ratio of said mixed polymer / catalyst is greater than 2.
2. Encre catalytique selon la revendication 1 , caractérisée en ce qu'elle comprend 5 % en masse d'un polymère mixte poly(3,4- éthylènedioxythiophène) poly(styrènesulfonate).2. Catalyst ink according to claim 1, characterized in that it comprises 5% by weight of a mixed polymer poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate).
3. Encre catalytique selon la revendication 1 ou 2, caractérisée en ce que le rapport en masse catalyseur/polymère mixte poly(3,4- éthylènedioxythiophène) poly(styrènesulfonate) est compris entre 0,01 et 1 inclus.3. Catalyst ink according to claim 1 or 2, characterized in that the mass ratio catalyst / mixed polymer poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) is between 0.01 and 1 inclusive.
4. Encre catalytique selon l'une quelconque des revendications précédentes caractérisée en ce que le rapport en masse catalyseur/polymère mixte poly(3,4-éthylènedioxythiophène) poly(styrènesulfonate) est de 0,1. 4. Catalytic ink according to any one of the preceding claims characterized in that the mass ratio catalyst / mixed polymer poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) is 0.1.
5. Utilisation de l'encre catalytique selon l'une quelconque des revendications précédentes pour la fabrication d'une électrode pour pile à combustible.5. Use of the catalytic ink according to any one of the preceding claims for the manufacture of a fuel cell electrode.
6. Utilisation de l'encre catalytique selon l'une quelconque des revendications 1 à 4 pour la fabrication d'un assemblage électrodes-membrane pour pile à combustible.6. Use of the catalytic ink according to any one of claims 1 to 4 for the manufacture of a membrane electrode assembly for fuel cells.
7. Utilisation de l'encre catalytique selon l'une quelconque des revendications 1 à 4 pour la fabrication d'une pile à combustible.7. Use of the catalytic ink according to any one of claims 1 to 4 for the manufacture of a fuel cell.
8. Procédé de dépôt d'une encre catalytique selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le dépôt est réalisé par jet d'encre. 8. Method of depositing a catalytic ink according to any one of claims 1 to 4, characterized in that the deposit is produced by ink jet.
PCT/FR2008/001417 2007-10-11 2008-10-09 Electrode comprising poly(3,4-ethylene dioxythiophene)/polystyrene sulfonate WO2009080920A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0707128 2007-10-11
FR0707128A FR2922369B1 (en) 2007-10-11 2007-10-11 ELECTRODE COMPRISING POLY (3,4-ETHYLENEDIOXYTHIOPHENE) POLY (STYRENESULFONATE)

Publications (2)

Publication Number Publication Date
WO2009080920A2 true WO2009080920A2 (en) 2009-07-02
WO2009080920A3 WO2009080920A3 (en) 2009-09-24

Family

ID=39433748

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR2008/001417 WO2009080920A2 (en) 2007-10-11 2008-10-09 Electrode comprising poly(3,4-ethylene dioxythiophene)/polystyrene sulfonate

Country Status (2)

Country Link
FR (1) FR2922369B1 (en)
WO (1) WO2009080920A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012051452A3 (en) * 2010-10-13 2012-06-07 Akamai Technologies, Inc. Protecting websites and website users by obscuring urls

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003087222A1 (en) * 2002-04-08 2003-10-23 Elecon, Inc. Conductive polymer compositions exhibiting n-type conduction
US20060052509A1 (en) * 2002-11-01 2006-03-09 Mitsubishi Rayon Co., Ltd. Composition containing carbon nanotubes having coating thereof and process for producing them

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003087222A1 (en) * 2002-04-08 2003-10-23 Elecon, Inc. Conductive polymer compositions exhibiting n-type conduction
US20060052509A1 (en) * 2002-11-01 2006-03-09 Mitsubishi Rayon Co., Ltd. Composition containing carbon nanotubes having coating thereof and process for producing them

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.M.SONG, S.Y.CHA, W.M.LEE: JOURNAL OF POWER SOURCES, vol. 94, 2001, pages 78-84, XP009101039 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012051452A3 (en) * 2010-10-13 2012-06-07 Akamai Technologies, Inc. Protecting websites and website users by obscuring urls

Also Published As

Publication number Publication date
WO2009080920A3 (en) 2009-09-24
FR2922369B1 (en) 2010-01-08
FR2922369A1 (en) 2009-04-17

Similar Documents

Publication Publication Date Title
KR100437293B1 (en) Polymer electrolytic fuel cell and method for producing the same
EP2559085B1 (en) Electrode structure for proton exchange membrane fuel cells
JP5108199B2 (en) POWDERED CATALYST MATERIAL, PROCESS FOR PRODUCING THE SAME, AND POLYMER FUEL CELL ELECTRODE
JP4987857B2 (en) Polymer dispersion and electrocatalyst ink
EP2800825B1 (en) Porous electrode for proton exchange membrane
EP3754770B1 (en) Method for forming a hydrophobic electrically conductive microporous layer for use as a gas-diffusion layer
CN1713423A (en) Electrode for fuel cell, membrane-electrode assembly for fuel cell comprising the same, fuel cell system comprising the same, and method for preparing the electrode
EP2893583B1 (en) Formulation of an active layer having improved performances
Pramanik et al. A study on process parameters of direct ethanol fuel cell
WO2009080920A2 (en) Electrode comprising poly(3,4-ethylene dioxythiophene)/polystyrene sulfonate
KR101229597B1 (en) Membrane electrode assembly for fuel cell and Method of preparing the same and Fuel cell comprising the same
US20190267636A1 (en) Enhancing catalyst activity of a pem fuel cell electrode with an ionic liquid additive
Koh et al. Effect of organic solvents on catalyst structure of PEM fuel cell electrode fabricated via electrospray deposition
JP2008177134A (en) Catalyst electrode for fuel cell, and its manufacturing method
JP7127603B2 (en) METHOD FOR MANUFACTURING ELECTRODE CATALYST LAYER FOR FUEL CELL
KR101153074B1 (en) Method of preparing a membrane electrode assembly for fuel cell and Fuel cell to which the method is applied
EP3120406B1 (en) Membrane-electrodes assembly for proton exchange membrane fuel cells (pemfc), and manufacturing method
KR20090047731A (en) Method of preparing the electrode for fuel cell and membrane electrode assembly and fuel cell comprising the electrode made by the same
KR101132459B1 (en) Method of preparing an electrode for fuel cell and Electrode prepared by the method and Membrane electrode assembly and Fuel cell comprising the same
CN111430727B (en) Thermocatalysis-assisted fuel cell electrode and preparation method and application thereof
KR101006006B1 (en) Electrode for fuel cell and Method of preparing the same and Membrane electrode assembly and Fuel cell comprising the same
EP4293762A1 (en) Formation of an mpl microporous layer on surface of an active layer for an electrochemical converter
RU2331144C1 (en) Cathode catalyst with lowered content of platinum for electrode of fuel cell
EP3570353A1 (en) Catalytic layers comprising a fullerene
FR3017747A1 (en) PROCESS FOR THE ELECTRODEPOSITION PREPARATION OF AN ELECTRODE MEMBRANE ASSEMBLY FOR A FUEL CELL

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08863705

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08863705

Country of ref document: EP

Kind code of ref document: A2