WO2016143348A1 - Encre catalytique de formation de couche de catalyseur d'électrode de pile à combustible à polymère solide, et procédé de fabrication de ladite encre catalytique - Google Patents

Encre catalytique de formation de couche de catalyseur d'électrode de pile à combustible à polymère solide, et procédé de fabrication de ladite encre catalytique Download PDF

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Publication number
WO2016143348A1
WO2016143348A1 PCT/JP2016/001346 JP2016001346W WO2016143348A1 WO 2016143348 A1 WO2016143348 A1 WO 2016143348A1 JP 2016001346 W JP2016001346 W JP 2016001346W WO 2016143348 A1 WO2016143348 A1 WO 2016143348A1
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WIPO (PCT)
Prior art keywords
polymer electrolyte
catalyst
fuel cell
catalyst ink
water
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PCT/JP2016/001346
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English (en)
Japanese (ja)
Inventor
直紀 浜田
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凸版印刷株式会社
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Publication of WO2016143348A1 publication Critical patent/WO2016143348A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a catalyst ink for forming an electrode catalyst layer of a polymer electrolyte fuel cell and a method for producing the same.
  • a polymer electrolyte fuel cell having a structure in which a polymer electrolyte membrane is sandwiched between a cathode electrode catalyst layer and an anode electrode catalyst layer operates at room temperature and has a short start-up time.
  • the electrode catalyst layer is manufactured by a method of applying and drying a catalyst ink to a polymer electrolyte membrane, a method of applying a catalyst ink to a transfer substrate, and then transferring the catalyst ink to a polymer electrolyte membrane.
  • the catalyst ink used in the above production is usually one in which carbon particles carrying a catalyst and a polymer electrolyte are dissolved in alcohol.
  • Patent Document 1 uses a method in which only water is used as a dispersion medium without using alcohol.
  • the dispersibility of the catalyst ink decreases, and cracks and pinholes are generated in the catalyst layer during coating and drying, leading to a decrease in power generation performance.
  • the application becomes impossible due to the repelling of the catalyst ink.
  • there is a method of preventing ignition by a method in which the catalyst is dissolved in water in advance and alcohol is added thereto but this method also causes the above problem because a large amount of water is required.
  • Patent Document 2 describes a method using t-butanol and 1-butanol as a dispersion medium.
  • t-butanol becomes a solid at room temperature, it is difficult to handle, and 1-butanol has a high boiling point, and it is necessary to set the drying temperature to a high temperature. May be reduced.
  • the present invention can reduce the risk of ignition during the production of a catalyst ink, and can be used to form an electrode catalyst layer of a polymer electrolyte fuel cell that can reduce the occurrence of cracks and pinholes during the coating and drying process. It is an object of the present invention to provide a catalyst ink and a method for producing the same.
  • a catalyst ink for forming an electrode catalyst layer of a polymer electrolyte fuel cell is a water-dispersed polymer electrolyte in which a polymer electrolyte having ion conductivity is dispersed in water.
  • a solution, catalyst-supporting carbon particles in which a catalyst is supported on a carbon particle carrier, and a dispersion medium in order to solve the above problems, a method for producing a catalyst ink for forming an electrode catalyst layer of a polymer electrolyte fuel cell according to one embodiment of the present invention comprises dispersing a polymer electrolyte having ion conductivity in water.
  • a step of obtaining a water-dispersed polymer electrolyte solution a step of mixing a catalyst-supported carbon particle having a catalyst supported on a carbon particle carrier and the water-dispersed polymer electrolyte solution to obtain a slurry, and diluting the slurry with a dispersion medium And mixing with the dispersion medium.
  • a water-dispersed polymer electrolyte solution obtained by dispersing a polymer electrolyte in water is obtained, and a slurry is obtained by adding the water-dispersed polymer electrolyte solution to catalyst-carrying carbon particles.
  • a catalyst ink is produced by diluting with a dispersion medium and mixing with the dispersion medium. Therefore, it is possible to reduce the risk of ignition during production with a small amount of water compared to the conventional case. Furthermore, since the amount of water can be reduced, it is possible to suppress a decrease in the dispersibility of the catalyst ink due to an increase in water concentration. As a result, it is possible to reduce the occurrence of cracks and pinholes when applying and drying the catalyst ink.
  • FIG. 1 is an exploded perspective view showing an example of the internal structure of the polymer electrolyte fuel cell according to the present embodiment.
  • a polymer electrolyte membrane 51 constituting a solid polymer fuel cell 50 has a pair of electrode catalyst layers 52A and 52F facing each other across the polymer electrolyte membrane 51 on both sides.
  • a gas diffusion layer 53A is provided on the surface of the electrode catalyst layer 52A opposite to the surface facing the polymer electrolyte membrane 51
  • a gas diffusion layer 53A is provided on the surface of the electrode catalyst layer 52F opposite to the surface opposite to the polymer electrolyte membrane 51.
  • the diffusion layer 53F is disposed so as to face each other across the polymer electrolyte membrane 51 and the pair of electrode catalyst layers 52A and 52F.
  • the surface of the gas diffusion layer 53A opposite to the surface facing the electrode catalyst layer 52A is provided with a gas flow channel 55A for reaction gas flow on the surface facing this surface, and cooling for circulating cooling water on the opposite main surface.
  • a separator 54A having a water passage 56A is disposed.
  • the surface of the gas diffusion layer 53F opposite to the surface facing the electrode catalyst layer 52F is provided with a gas flow channel 55F for reaction gas flow on the surface facing this surface, and the coolant flow is provided on the opposite main surface.
  • a separator 54F having a cooling water passage 56F is disposed.
  • the electrode catalyst layers 52A and 52F may be simply referred to as “electrode catalyst layer 52”.
  • FIG. 2 is a diagram illustrating a manufacturing process of the catalyst ink according to the present embodiment. As shown in FIG. 2, first, a polymer electrolyte having ion conductivity is dispersed in water to obtain a water-dispersed polymer electrolyte solution.
  • a slurry (hereinafter may be referred to as “polymer electrolyte slurry”) is obtained by adding and mixing the water-dispersed polymer electrolyte solution to the catalyst-supported carbon particles in which the catalyst is supported on the carbon particle carrier.
  • polymer electrolyte slurry a slurry
  • the risk of ignition can be reduced with a smaller amount of water than the method of adding water alone.
  • a planetary mixer, a dissolver, a kneader or the like can be used.
  • the catalyst-supporting carbon particles carbon black (platinum-supporting carbon particles) in which platinum is supported as a catalyst on a carbon particle support is used.
  • the concentration of the water-dispersed polymer electrolyte solution used in the present embodiment is such that the water concentration in the finally provided catalyst ink is in the range of 10% by mass to 35% by mass, preferably 15% by mass to 30% by mass. Adjust so that it is within the following range. In this embodiment, if the water concentration is too low, specifically, if it is less than 10% by mass, the risk of ignition may increase. In the present embodiment, if the water concentration is too high, specifically, if it exceeds 35% by mass, the dispersibility of the catalyst ink is lowered, and cracks and pinholes are likely to occur during coating and drying.
  • the dry mass value (equivalent weight; EW (Equivalent Weight)) per mole of the proton donating group of the polymer electrolyte used for the production of the catalyst ink is in the range of 500 (g / eq) to 800 (g / eq).
  • EW Equivalent Weight
  • the dry mass value (equivalent weight; EW) per mole of the proton donating group is the mass of the proton conducting material per unit mole of the introduced proton donating group, and the smaller the value, the proton conducting material. It indicates that the ratio of proton donating groups is high.
  • a polymer material having proton conductivity for example, a fluorine-based polymer electrolyte or a hydrocarbon-based polymer electrolyte is used.
  • commercially available aqueous dispersions of polymer electrolytes can also be used, but if the dispersion medium contains a small amount of alcohol, the catalyst-carrying carbon particles are pre-moistened with water to prevent ignition. Risk can be reduced. If the ratio of the polymer electrolyte to the carbon particle carrier is too small, specifically, if it is less than 0.9, the proton transport resistance increases, causing a decrease in power generation performance, and the strength of the coating film becomes weak at the time of application. Cause cracking.
  • the weight ratio which is the ratio of the polymer electrolyte to the carbon particle carrier, is set in the range of 0.9 to 1.5.
  • the catalyst ink is manufactured by diluting and mixing the polymer electrolyte slurry manufactured by the above process with a dispersion medium.
  • the dispersion medium used for dilution / mixing include alcohols (organic solvents) such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, and pentanol. Any one of these can be selected and used.
  • a planetary mixer, a dissolver, a bead mill, and the like can be used. Among them, it is preferable to use a bead mill.
  • a polymer electrolyte slurry is prepared by adding a water-dispersed polymer electrolyte solution, in which a polymer electrolyte having ion conductivity is dispersed in water, to catalyst-supported carbon particles in which a catalyst is supported on a carbon particle carrier during the production of a catalyst ink.
  • a water-dispersed polymer electrolyte solution in which a polymer electrolyte having ion conductivity is dispersed in water
  • catalyst-supported carbon particles in which a catalyst is supported on a carbon particle carrier during the production of a catalyst ink.
  • the concentration of the water-dispersed polymer electrolyte solution is set so that the final catalyst ink has a water concentration in the range of 10% by mass to 35% by mass, a catalyst ink having a good dispersion state can be obtained. This makes it possible to reduce the occurrence of cracks and pinholes during application and drying.
  • a dispersion medium containing one or more solvents belonging to alcohols is used as a dispersion medium for diluting and mixing the polymer electrolyte slurry, the polymer electrolyte can be sufficiently dissolved, and the catalyst It becomes possible to ensure relatively good dispersibility of the supported carbon particles.
  • alcohol since alcohol has a low boiling point, it becomes possible to reduce energy required in the drying step.
  • the dry mass value (equivalent weight; EW) per mole of the proton-donating group of the polymer electrolyte was set within the range of 500 (g / eq) to 800 (g / eq)
  • the dry mass value was When it is too small, specifically, less than 500 (g / eq), the catalyst layer becomes more hydrophilic, and flooding occurs during power generation, and it is possible to suppress a decrease in power generation performance.
  • the dry mass value is too large, specifically, exceeding 800 (g / eq)
  • the bond between the carbon particles is weakened, the strength of the coating film is weakened at the time of application, and cracks are generated. It becomes possible to suppress.
  • the weight ratio which is the ratio of the polymer electrolyte to the carbon particle carrier, is in the range of 0.9 to 1.5, so that the weight ratio is too small, specifically less than 0.9. It is possible to suppress a decrease in gas permeability and a decrease in coating strength at the time of application, which are caused by the above. In addition, it is possible to suppress a decrease in gas permeability and a decrease in power generation performance caused by an excessively large weight ratio, specifically, exceeding 1.5.
  • Example 2 Next, a second embodiment of the present invention will be described.
  • the catalyst of Example 2 was the same as Example 1 except that the final water concentration in the catalyst ink was 20% and the mass ratio (I / C) of the polymer electrolyte to carbon was 1.2. Ink was obtained. The catalyst ink of Example 2 did not ignite during the production process, and the electrode catalyst layer obtained by coating and drying was satisfactory without defects such as cracks and pinholes.
  • Example 3 Next, a third embodiment of the present invention will be described. A catalyst ink of Example 3 was obtained in the same manner as in Example 1 except that the final water concentration in the catalyst ink was 15% and 1-butanol was used as a dispersion medium for diluting the slurry. The catalyst ink of Example 3 did not ignite during the production process, and the electrode catalyst layer obtained by coating and drying was satisfactory without defects such as cracks and pinholes.
  • Comparative Example 1 A catalyst ink of Comparative Example 1 was obtained in the same manner as in Example 1 except that the final water concentration in the catalyst ink was 5%. In the production process of the catalyst ink of Comparative Example 1, good catalyst-carrying carbon particles and a polymer electrolyte slurry could not be obtained, and when a dispersion medium was added for dilution, heat generation was confirmed.
  • Comparative Example 2 A catalyst ink of Comparative Example 2 was obtained in the same manner as in Example 1 except that the mass ratio (I / C) of the polymer electrolyte to carbon was 0.6. The catalyst ink of Comparative Example 2 did not ignite during the production process, but cracks and pinholes were confirmed in the electrode catalyst layer obtained by coating and drying.
  • Comparative Example 3 A catalyst ink of Comparative Example 3 was obtained in the same manner as in Example 1 except that the equivalent weight of the polymer electrolyte was 1000 (g / eq). The catalyst ink of Comparative Example 3 did not ignite during the production process, but cracks and pinholes were confirmed in the electrode catalyst layer obtained by coating and drying.
  • SYMBOLS 50 Solid polymer fuel cell 51 ... Polymer electrolyte membrane 52A, 52F ... Electrode catalyst layer 53A, 53F ... Gas diffusion layer 54A, 54F ... Separator 55A, 55F ... Gas flow path 56A, 56F ... Cooling water path

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

Abstract

L'invention concerne une encre catalytique pour former une couche de catalyseur d'électrode d'une pile à combustible à polymère solide, avec laquelle il est possible de réduire le risque d'allumage lors de la fabrication de l'encre catalytique et de réduire l'incidence de fissures et de formation de trous d'épingles pendant les étapes d'application et de séchage. La présente invention concerne également un procédé de fabrication de ladite encre catalytique. Selon un mode de réalisation de la présente invention, l'encre catalytique est fabriquée par l'ajout d'une solution d'électrolyte polymère en dispersion aqueuse, dans laquelle un polyélectrolyte est dispersé dans de l'eau, à des particules de carbone portant un catalyseur dans lesquelles un catalyseur est porté sur un véhicule particulaire de carbone pour obtenir une bouillie, et la bouillie est diluée à l'aide d'un milieu de dispersion et mélangée avec le milieu de dispersion.
PCT/JP2016/001346 2015-03-12 2016-03-10 Encre catalytique de formation de couche de catalyseur d'électrode de pile à combustible à polymère solide, et procédé de fabrication de ladite encre catalytique WO2016143348A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-049393 2015-03-12
JP2015049393A JP6569251B2 (ja) 2015-03-12 2015-03-12 固体高分子形燃料電池の電極触媒層形成用の触媒インク及びその製造方法

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WO2016143348A1 true WO2016143348A1 (fr) 2016-09-15

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CN114388820A (zh) * 2021-12-09 2022-04-22 同济大学 一种燃料电池用催化剂浆料及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001266901A (ja) * 2000-03-22 2001-09-28 Toyota Motor Corp 燃料電池用の電極触媒溶液およびその製造方法
JP2005310545A (ja) * 2004-04-21 2005-11-04 Matsushita Electric Ind Co Ltd 高分子電解質型燃料電池の製造方法
JP2008031464A (ja) * 2006-07-04 2008-02-14 Sumitomo Chemical Co Ltd 高分子電解質エマルションおよびその用途
WO2009116630A1 (fr) * 2008-03-21 2009-09-24 旭硝子株式会社 Ensemble membrane-électrode pour pile à combustible à polymère solide, et pile à combustible à polymère solide
JP2009218006A (ja) * 2008-03-07 2009-09-24 Nissan Motor Co Ltd 電解質膜−電極接合体の製造方法
JP2012004048A (ja) * 2010-06-18 2012-01-05 Asahi Kasei E-Materials Corp 電解質膜並びにその製造方法、電極触媒層並びにその製造方法、膜電極接合体、及び、固体高分子電解質型燃料電池
JP2012069276A (ja) * 2010-09-21 2012-04-05 Toyota Motor Corp 燃料電池用電極の製造方法
JP2013225433A (ja) * 2012-04-23 2013-10-31 Nippon Steel & Sumitomo Metal 燃料電池

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001266901A (ja) * 2000-03-22 2001-09-28 Toyota Motor Corp 燃料電池用の電極触媒溶液およびその製造方法
JP2005310545A (ja) * 2004-04-21 2005-11-04 Matsushita Electric Ind Co Ltd 高分子電解質型燃料電池の製造方法
JP2008031464A (ja) * 2006-07-04 2008-02-14 Sumitomo Chemical Co Ltd 高分子電解質エマルションおよびその用途
JP2009218006A (ja) * 2008-03-07 2009-09-24 Nissan Motor Co Ltd 電解質膜−電極接合体の製造方法
WO2009116630A1 (fr) * 2008-03-21 2009-09-24 旭硝子株式会社 Ensemble membrane-électrode pour pile à combustible à polymère solide, et pile à combustible à polymère solide
JP2012004048A (ja) * 2010-06-18 2012-01-05 Asahi Kasei E-Materials Corp 電解質膜並びにその製造方法、電極触媒層並びにその製造方法、膜電極接合体、及び、固体高分子電解質型燃料電池
JP2012069276A (ja) * 2010-09-21 2012-04-05 Toyota Motor Corp 燃料電池用電極の製造方法
JP2013225433A (ja) * 2012-04-23 2013-10-31 Nippon Steel & Sumitomo Metal 燃料電池

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JP2016170949A (ja) 2016-09-23

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