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WO2006080159A1 - Film electrolytique conducteur de protons, procede pour le fabriquer et pile a combustible de type polymere solide utilisant ledit film electrolytique conducteur de protons - Google Patents

Film electrolytique conducteur de protons, procede pour le fabriquer et pile a combustible de type polymere solide utilisant ledit film electrolytique conducteur de protons Download PDF

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Publication number
WO2006080159A1
WO2006080159A1 PCT/JP2005/023223 JP2005023223W WO2006080159A1 WO 2006080159 A1 WO2006080159 A1 WO 2006080159A1 JP 2005023223 W JP2005023223 W JP 2005023223W WO 2006080159 A1 WO2006080159 A1 WO 2006080159A1
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Prior art keywords
proton
electrolyte membrane
group
particles
proton conductive
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PCT/JP2005/023223
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English (en)
Japanese (ja)
Inventor
Takayuki Suzuki
Takato Chiba
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to JP2007500436A priority Critical patent/JP4957544B2/ja
Publication of WO2006080159A1 publication Critical patent/WO2006080159A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • 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
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • 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
    • H01M8/1037—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes
    • 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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • 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
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. in situ polymerisation or in situ crosslinking
    • H01M8/1074—Sol-gel processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—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

  • PROTON CONDUCTIVE ELECTROLYTE MEMBRANE MANUFACTURING METHOD THEREOF, AND SOLID POLYMER TYPE FUEL CELL USING THE PROTON CONDUCTIVE ELECTROLYTE MEMBRANE
  • the present invention relates to a proton conductive electrolyte membrane and a method for producing a proton conductive electrolyte membrane, and more particularly to a polymer electrolyte fuel cell using the proton conductive electrolyte membrane as a fuel cell electrolyte.
  • a fuel cell is a power generation device that generates electricity by reacting hydrogen and oxygen, and only water is generated by the power generation reaction. It has excellent properties! It is attracting attention as an energy-saving technology that deals with environmental problems such as the destruction of the ozone layer and V.
  • solid polymer fuel cells There are four types of fuel cells: solid polymer fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells, and solid oxide fuel cells.
  • solid polymer fuel cells have the advantages of low operating temperature and solid electrolyte (polymer thin film).
  • the polymer electrolyte fuel cell is a reforming type that converts methanol into hydrogen using a reformer, a direct methanol type that uses methanol directly without using a reformer (DMFC, Direct Methanol Polymer Fuel Cell),
  • DMFC Direct Methanol Polymer Fuel Cell
  • D MFC does not require a reformer, so it can be made compact and lightweight.
  • PDA Personal Information terminals
  • dedicated batteries for the upcoming ubiquitous society, Its practical application is expected.
  • Main components of the polymer electrolyte fuel cell are an electrode, a catalyst, an electrolyte, and a separator.
  • a polymer proton-conducting electrolyte membrane is used as the electrolyte.
  • Proton-conducting electrolyte membranes are used for applications such as ion exchange membranes and humidity sensors, but in recent years, they are also attracting attention as applications as electrolytes in solid polymer fuel cells.
  • a sulfonic acid group-containing fluororesin membrane represented by DuPont's Nafion (registered trademark) has been studied for use as an electrolyte in a portable fuel cell.
  • An electrolyte membrane in which the pores of a substantially non-swelled porous substrate are filled with a polymer having proton conductivity is disclosed (for example, see Patent Document 2).
  • a porous substrate Inorganic materials such as ceramic, glass and alumina, or heat-resistant polymers such as polytetrafluoroethylene and polyimide are used. It is described that the porous substrate preferably has a porosity of 10 to 95%, an average pore diameter of 0.001 to 100 / ⁇ ⁇ , and a thickness of several / zm.
  • a polymer having a phosphoric acid group, a phosphonic acid group or a phosphinic acid group in the side chain is provided in the pores of the porous membrane.
  • the porous membrane include ultra high molecular weight polyolefin resin and fluorine resin. It is described that the porous membrane preferably has a porosity of 30 to 85%, an average pore diameter of 0.005 to 10 / ⁇ ⁇ , and a thickness of 5 to 500 m.
  • Patent Document 1 JP-A-10-312815
  • Patent Document 2 Pamphlet of International Publication No. 00Z54351
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-83514
  • Non-Patent Document 1 Electrochemistry, 70, 934 (2002)
  • the first object of the present invention is to provide a proton conductive electrolyte membrane having sufficiently high proton conductivity and sufficiently low methanol permeability, and has such excellent performance.
  • An object of the present invention is to provide a method for producing a proton conductive electrolyte membrane.
  • a second object of the present invention is to provide a polymer electrolyte fuel cell having, as an electrolyte, a proton conductive electrolyte membrane having excellent performance as described above.
  • R 1 represents an alkyl group having 4 or less carbon atoms
  • R 2 represents a copolymerizable organic group
  • the membrane is a polymer obtained by copolymerizing at least the compounds (a) to (c) and (d) a reactive emulsifier.
  • the inorganic porous membrane is obtained by forming a layer containing the inorganic particles and the organic particles using a dispersion containing inorganic particles and organic particles, and then firing the layer.
  • R 2 is an organic group containing at least one of an epoxy group, a styryl group, a methacryloxy group, an atalyoxy group or a bur group.
  • the proton conductive electrolyte membrane according to any one of 1 to 6.
  • the proton conductive electrolyte membrane according to any one of 1 to 9 is used as the electrolyte.
  • the pores of the inorganic porous membrane are filled with at least the compounds (a) to (c) and (d) a reactive emulsifier, and subjected to in-situ polymerization. Production method for proton conducting electrolyte membranes.
  • the dispersion containing the inorganic particles and the organic particles contains 5 to 60% by volume of the inorganic particles and 40 to 95% by volume of the inorganic particles (the total volume of the inorganic particles and the organic particles is 1 11.
  • a proton conductive electrolyte membrane having a sufficiently high proton conductivity and a sufficiently low methanol permeability, a method for producing the same, and a solid polymer fuel cell using the proton conductive electrolyte membrane are provided.
  • a method for producing the same and a solid polymer fuel cell using the proton conductive electrolyte membrane are provided.
  • FIG. 1 is a schematic view showing one embodiment of a direct methanol solid polymer fuel cell of the present invention.
  • FIG. 2 is a schematic view of an H-type cell for evaluating methanol permeability.
  • the proton conductive electrolyte membrane of the present invention includes a step of forming a layer containing a dispersion containing inorganic particles and organic particles, a step of drying and firing the layer, and an inorganic obtained by the step of firing. And a step of filling the pores of the porous membrane with a proton conductive polymer.
  • a support may be used.
  • the support that is eventually burned out or melted away, or that can be peeled off.
  • Any support material can be used as long as it is present.
  • a support material made of any material such as paper such as filter paper, cloth such as nonwoven fabric, polymer film such as polyethylene terephthalate can be used.
  • the surface of the support is preferably smooth, and if it is smooth, the surface of the proton-conducting electrolyte membrane obtained is also smooth, and when it is used as an electrolyte for a solid polymer fuel cell, the electrode and the proton-conducting electrolyte Close contact at the interface with the membrane.
  • the surface roughness of the support is not particularly limited, but the surface roughness Rz of the surface of the layer containing the formed inorganic particles and organic particles is preferably 3 m or less.
  • the surface roughness Rzi is the ten-point average surface roughness Rz defined by IS B 0601.
  • a stylus type three-dimensional roughness meter (Surfcom 570A) manufactured by Tokyo Seimitsu Co., Ltd.
  • the side opposite to the surface on which the layer containing the dispersion is formed is used. It may be preferable to provide a backing layer on the surface.
  • Inorganic particles include silica (SiO 2), alumina (Al 2 O 3), zirconium oxide (ZrO 2), acid
  • Silica (SiO 2) is preferred.
  • silica (SiO 2) amorphous silica is preferred.
  • the production method may be any of the formula method, the wet method, and the air-mouth gel method, the wet method of colloidal silica is more preferable.
  • the average particle diameter of the inorganic particles is preferably 10 nm or more, more preferably 10 to 100 nm, and even more preferably 10 to 50 nm.
  • the average particle size of the inorganic particles can be determined by observing with a scanning electron microscope, for example. Therefore, the major axis of 200 particles can be measured and the average particle diameter can be obtained.
  • organic particles organic particles of any material can be used as long as they are eventually burned out or dissolved, but they do not swell or dissolve in the solvent as a dispersion medium used in the dispersion. Those are preferred.
  • an aqueous solvent is preferred as the dispersion medium.
  • the organic particles include acrylic resin, styrene resin, styrene Z acrylic resin, styrene Z dibutene benzene resin, and polyester resin.
  • polymer beads such as urethane-based resin can be used.
  • the average particle diameter of the organic particles is preferably 10 to 450 nm, and more preferably 100 to 300 nm.
  • the inorganic porous membrane of the present invention is prepared by preparing a dispersion containing inorganic particles and organic particles throughout the production process and using this to form a layer containing inorganic particles and organic particles.
  • a dispersion medium of the dispersion those described below can be used, and as a method for forming the layer, the method described below can be used.
  • the inorganic particles are fixed and sintered to form a thin film.
  • the particles occupy! /, And the part forms pores in the thin film (in the layer).
  • the average pore diameter (average pore diameter) of the inorganic porous membrane is preferably 10 to 450 nm, more preferably 100 to 300 nm.
  • the average pore diameter can be determined by mercury porosimetry using, for example, a pore sizer 9320 manufactured by Shimadzu Corporation.
  • the proton conductive electrolyte membrane obtained by filling the thus formed inorganic porous membrane with a proton conductive polymer was found to have high proton conductivity and low methanol permeability.
  • the porosity of the inorganic porous membrane is preferably 40 to 95%, more preferably 50 to 70%.
  • the porosity in the present invention is the following calculation in a state (inorganic porous film) obtained by forming a layer using a dispersion containing inorganic particles and organic particles and firing as described above. The value obtained by the formula.
  • the porosity can be calculated by the following equation: mass W (g) per unit area S (cm 2 ), average thickness t ( ⁇ m) and density d (g / cm 3 ) force of the inorganic porous membrane .
  • Porosity (%) (1— (10 4 'WZ (S't'd))) X 100
  • the dispersion containing the inorganic particles and organic particles Te per cent ⁇ For the inorganic particles and organic particles, inorganic particles 5 to 60 volume 0/0, used in a proportion of the organic particles 40 to 95 vol 0/0 ( By setting the total volume of inorganic particles and organic particles to 1, the porosity of the inorganic porous membrane can be adjusted to the above range.
  • the volume% expresses the ratio of the volume of each particle to the sum of the volume of the inorganic particles and the volume of the organic particles as a percentage.
  • the inorganic porous membrane After being filled with the proton conductive polymer of the present invention, the inorganic porous membrane is obtained by using the area ratio of the polymer portion to the other portion in the cross-sectional photograph using a scanning electron microscope.
  • the porosity of the film can be approximated.
  • the rate value is preferably 40 to 95%, more preferably 50 to 70%.
  • the preferred range of the ratio of the inorganic particles to the organic particles is as described above, but the solid content concentration of the dispersion (that is, the inorganic particles and organic particles, or other content further contained in these as required)
  • the solid component including the component is preferably 5 to 80% by mass, preferably 10 to 40% by mass.
  • the solid content concentration is preferably 0.01 to 20% by mass! /.
  • the dispersion medium is preferably an aqueous solvent.
  • aqueous solvent various known solvents such as water and alcohols can be used, but water or a mixed solvent containing water as a main component is preferably used.
  • Examples of the dispersion aid for dispersing inorganic particles and organic particles include higher fatty acid salts, alkyl sulfates, alkyl ester sulfates, alkyl sulfonates, sulfosuccinates, naphthalene sulfonates, and alkyl phosphates.
  • Various surfactants such as salts, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkyl phenyl ethers, polyoxyethylene polyoxypropylene glycols, glycerin esters, sorbitan esters, polyoxyethylene fatty acid amides, amine oxides may be used. it can.
  • Examples of the dispersing method include ball mill, sand mill, attritor, roll mill, Examples include a method using a theta, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, and the like, and these methods can be used alone or in appropriate combination.
  • the dispersion is filtered with a membrane filter using a vacuum suction filter, and the layer containing inorganic particles and organic particles is placed on the membrane filter.
  • a method of depositing and drying the film and peeling off the membrane filter or a method of applying the dispersion to a support and drying.
  • a method in which the dispersion is applied to a support is preferable.
  • a coating method for example, a conventionally known coating method such as a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, an etching method or the like can be adopted. .
  • the formation of the layer containing inorganic particles and organic particles may be performed by one application or vacuum suction filtration, but may be formed in multiple layers.
  • an inorganic porous film having a multilayer structure with different porosity and the like can be obtained by controlling the types and particle sizes of the inorganic particles and organic particles forming each layer.
  • the inorganic porous film is indispensable on the support.
  • grains should just be heat-processed with an electric furnace etc. in inert gas, for example, nitrogen atmosphere, and may be baked.
  • the heat treatment can be performed using, for example, an electric furnace equipped with a heating element such as molybdenum silicide, and can be performed at 1500 ° C. or less, more preferably at 400 to 1300 ° C.
  • the time for heating can be appropriately set depending on the size of the target inorganic porous film.
  • a heating time of about 5 to 24 hours can be used. If the heating time is long, the sintering proceeds and the average pore diameter may be reduced.
  • the temperature increase rate and temperature decrease rate in the heat treatment for obtaining the inorganic porous membrane can be appropriately set. It is preferable that the temperature rise rate and the temperature fall rate be 100 to 300 ° CZ time. It is also preferable to perform the heat treatment in two steps, ie, pre-baking and main baking, or more than two times.
  • the proton conductive polymer filled in the pores of the inorganic porous membrane according to the present invention has at least (a) one or more sulfonic acid groups and one or more ethylenic groups in the molecule.
  • a compound having a saturated bond (b) a compound having one or more phosphate groups and one or more ethylenically unsaturated bonds in the molecule, and (c) a compound represented by the general formula (1). It is characterized by being a polymer obtained by copolymerization, and at least (a) a compound having at least one sulfonic acid group and at least one ethylenically unsaturated bond in the molecule, and (b) a molecule.
  • the compound having one or more sulfonic acid groups and one or more ethylenically unsaturated bonds in the molecule is not particularly limited.
  • the compounds having one or more sulfonic acid groups and one or more ethylenically unsaturated bonds in these molecules may be used alone or in combination of two or more.
  • Examples of the other unsaturated compound that can be copolymerized include (meth) acrylonitrile, among all the unsaturated compounds having at least one ethylenically unsaturated bond in the molecule. (Meth) acrylic acid esters and substituted or unsubstituted styrenes are preferred. Furthermore, ethylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, hexamethyl diol di (meth) acrylate which contains multiple ethylenically unsaturated bonds in one molecule. Butylbenzene, N, N-methylenebisatyramide, etc. form a cross-linked structure and are preferably used to improve the durability of the electrolyte membrane.
  • the compound having one or more phosphate groups and one or more ethylenically unsaturated bonds in the molecule is not particularly limited, but preferably a compound represented by the following general formula (2): I can list them. [0042] [Chemical 2]
  • R 3 represents a hydrogen atom or a methyl group
  • X represents a divalent organic group, specifically an alkylene group or an arylene group, preferably an ethylene group or a propylene group.
  • p represents an integer of 1 or more, preferably an integer of 1 to 10.
  • Specific examples of the compound represented by the general formula (2) include methacryloxetyl phosphate, methacryloyl di (oxyethylene) phosphate, methacryloyl tri (oxyethylene) phosphate, methacryloyl tetra (oxyethylene) phosphate, and metathalloyl.
  • R 1 of the compound represented by the general formula (1) represents an alkyl group having 4 or less carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Have group May be.
  • R 2 represents a copolymerizable organic group, and preferably includes at least one of an epoxy group, a styryl group, a methacryloxy group, an alicyclic group or a bur group. It is an organic group.
  • Specific examples of the compound represented by the general formula (1) include butyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxy cyclohexylene) ethynoletrimethoxysilane, 3g
  • silyl group of the compound represented by the general formula (1) can react to form a crosslinked structure, or the silyl group can react with and bind to the surface silanol group of the inorganic porous membrane.
  • the proton conductive polymer has a cross-linked structure.
  • the cross-linked structure is preferably obtained by the reaction of the silyl group. It is also preferable to form a crosslinked structure using a so-called crosslinking agent.
  • cross-linking agents include ethylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, hexamethylene diol di (meth) acrylate, etc. containing multiple ethylenically unsaturated bonds in one molecule. N, N-methylenebisacrylamide, dibutenebenzene and the like.
  • crosslinked structure when the above-mentioned crosslinked structure is formed, in the case of in-situ polymerization described later, it is preferable to form the crosslinked structure at the same time when copolymerizing the peptone conductive polymer.
  • a proton conductive polymer is copolymerized and filled as a solution into the pores of an inorganic porous membrane, it is preferable to fill and crosslink the force.
  • an ionic emulsifier having at least one unsaturated double bond in the molecule and a Z or nonionic emulsifier is preferably used.
  • the reactive emulsifier is preferably a compound having at least one hydrophobic group, hydrophilic group and reactive group in the molecule.
  • the hydrophobic group is an aliphatic or aromatic hydrocarbon group
  • the hydrophilic group is Nonionic groups such as polyoxyalkylene ether groups, sulfonates, Contains ionic groups such as sulfonate and phosphate, and the reactive group contains butyl ether group, allylic ether group, butyl ether group, aralkyl ether group, allyloyl group, and methacryloyl group. Things are preferred.
  • Examples of the reactive emulsifier include those disclosed in JP-A-62-22803, 62-104802, 62-104803, 62-221431, and 62-221432. 62-225237, 62-244430, 62-286528, 62-289228, 62-289229, 63-12334, 63-54 930 63-77530, 63-77531, 63-77532, 63-84624, 63-84625, 63-126535, 63-126536, 63-147530, 63-319035, JP-A-1-11 630, 1-222338, 1-222627, 1-222628, 1-30632 1-34430, 1-34431, 1-34432, 1-99638, 1-99639, 4-50204, 4-5380 2 Gazette, 4-4-1401 Those that have been, and the like.
  • the reactive emulsifier include, for example, 1- (meth) atarioxy-2-hydroxypropane, (meth) atarioxy-2-hydroxypropane, (meth) ataryloxy Bonylmethyl 3 alkoxy (polyoxyalkylenoxy) 2 hydroxypropane, alkylphenoxy (polyoxyalkylenoxy) 2-hydroxypropane or acyloxy (polyoxyalkylenoxy) 2-hydroxypropane or its alkylene oxide adducts
  • These are sulfuric acid or phosphoric acid esters or salts thereof, alkylene oxide adducts of bisphenol compounds or glycol compounds, or sulfuric acid or phosphoric acid esters or salts thereof, alkylene oxide adducts of bur or aryl phenol compounds or These sulfur Or phosphoric acid ester, or a salt thereof, Monoariru one monoalkyl ester or a salt thereof Suruhokoha click acid, a sulfosuccinic acid mono
  • “Adekalia Soap NE”, “Adekalia Soap SE”, “Adekalia Soap ER”, “Adekalia Soap SR”, “Adekalia Soap PP”, “Adekalia Soap PPE” Product Name, manufactured by Asahi Denki Co., Ltd.), "Aquaron KH”, “Aquaron HS”, “Aquaron BC”, “Aqua Kun RN”, “New Frontier” ), “Eleminol ES”, “Eleminol JS”, “Eleminol RS”, “Eleminol MON”, “Eleminol HA” (trade name, manufactured by Sanyo Chemical Industries), “Latemul” (trade name, Kao Corporation) But not limited to these. These reactive emulsifiers may be used alone or in combination of two or more.
  • the method of filling the pores of the inorganic porous membrane with the proton conductive polymer is not particularly limited.
  • the proton conductive polymer can be filled into the pores of the inorganic porous membrane by, for example, a method of immersing in the proton conductive polymer solution.
  • the proton conductive polymer can be easily filled in the pores by using ultrasonic waves or reducing the pressure.
  • the solvent used in the proton conductive polymer solution is preferably a solvent that has a low boiling point immediately after removal in the subsequent drying step, and that can be recovered and reused.
  • a solvent that has a low boiling point immediately after removal in the subsequent drying step and that can be recovered and reused.
  • alcohols, tetrahydrofuran It is preferable to use acetone, ethyl acetate or the like.
  • a precursor of the proton conductive polymer (the compound represented by the general formula (1), 1 in the molecule) A compound having one or more sulfonic acid groups and one or more ethylenically unsaturated bonds, a compound having one or more phosphoric acid groups and one or more ethylenically unsaturated bonds in the molecule, a reactive emulsifier, Other unsaturated compounds that can be polymerized, etc.) and a solution containing a polymerization initiator are filled in the pores of the inorganic porous membrane, and then subjected to a suitable method known in the art such as thermal polymerization or photopolymerization.
  • a suitable method known in the art such as thermal polymerization or photopolymerization.
  • This is a method of polymerizing into a proton conductive polymer by in situ polymerization. At that time, it is possible to easily fill the pores with a solution containing the precursor of the proton conductive polymer and the polymerization initiator by using ultrasonic waves or reducing the pressure. After hydrophilizing the pore surface of the inorganic porous membrane, the solution containing the proton conductive polymer precursor and the polymerization initiator is filled into the pores of the inorganic porous membrane, and in-situ polymerization is performed. A method is also preferred. Moreover, it is also preferable to adjust the viscosity of the solution containing the proton conductive polymer precursor and the polymerization initiator as appropriate so that the pores can be easily filled.
  • a part of the monomer may be prepolymerized, or a small amount of an appropriate polymer may be added and dissolved.
  • dilute by adding an appropriate solvent to lower the viscosity.
  • the filling rate of the proton conductive polymer is preferably 80 to 100%.
  • the filling rate is the difference between the total area of the filled proton conductive polymer with respect to the total area of the voids of 100 voids when measured using a tomographic photograph of the proton conductive electrolyte membrane. Refers to the ratio.
  • the thermal polymerization initiator preferably the thermal polymerization initiator or the photopolymerization initiator, is a compound capable of generating a polymerizable radical by applying thermal energy.
  • azobis-tolyl compounds such as 2,2′-azobisisobutyric-tolyl, 2,2′-azobispropio-tolyl, benzoyl peroxide, lauryl peroxide, acetylyl peroxide, T-Butyl perbenzoate, a cumyl hydroperoxide, di-t-butyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, peracids, alkyl peroxyl rubamates, nitro sularyl acyla Organic peracids such as amines, potassium persulfate, ammonium persulfate, inorganic peroxides such as potassium perchlorate, diazoaminobenzene, p-trobenzenediazome, azobis substitution Azo or diazo compounds such as alkanes, diazothioethers, and arylazosulfones, nitros
  • the polymerization initiator is usually 0.1 to 30% by mass in the total polymerizable composition.
  • the range of 0.5 to 20% by mass is more preferable.
  • the amount of the photopolymerization initiator used is in the range of 0.5 to 5% by mass, preferably in the range of 1 to 3% by mass, based on the total mass of the unsaturated compounds.
  • the proportion of each component when copolymerizing the proton conductive polymer of the present invention is as follows: (c) the compound represented by the general formula (1); and (a) one or more compounds in the molecule.
  • the mass ratio of the compound having a sulfonic acid group and one or more ethylenically unsaturated bonds is preferably in the range of 1: 100 to 1: 1.
  • the mass ratio of (c) the compound represented by the general formula (1) and (b) the compound having one or more phosphate groups and one or more ethylenically unsaturated bonds in the molecule is 1: A range of 100 to 1: 1 is preferred.
  • the mass ratio with the compound having an ethylenically unsaturated bond is preferably in the range of 100: 10 to 1: 1.
  • the mass ratio of the (d) reactive emulsifier to the compound represented by (c) the general formula (1) is preferably in the range of 1: 100 to 100: 1.
  • the proton-conducting polymer has an ion exchange capacity of 0.5 to 5.0 milliequivalent Zg dry resin, preferably 1.0 to 4.5 milliequivalent Zg dry resin.
  • the ion exchange capacity is less than 0.5 meq Zg dry resin, the ion conduction resistance increases, and when it is greater than 4.5 meq Zg dry resin, it becomes easier to dissolve in water.
  • the ion exchange capacity can be determined by the following measurement method. First, the proton conductive polymer is immersed in a 2 mol ZL salt / sodium aqueous solution for about 5 minutes to replace the proton of the acidic group with sodium. Neutralization titration with sodium hydroxide and sodium hydroxide of known concentration is performed on protons liberated in the solution by sodium substitution. Then, the dry weight (W) of the proton-conducting polymer and the volume of sodium hydroxide (V) force proton (H +) required for neutralization titration were calculated, and the ion exchange capacity (meqZg ) The following formula is An example of neutralization titration with 0.05 mol ZL NaOH aqueous solution is shown.
  • the average film thickness of the proton conductive electrolyte membrane of the present invention is not particularly limited, but is usually 500 m or less, preferably 300 ⁇ m or less, more preferably 50 to 200 ⁇ m.
  • the average film thickness can be obtained by measuring five points at any point and calculating the average.
  • the proton conductive electrolyte membrane of the present invention can be used in a fuel cell.
  • fuel cells a methanol fuel cell is preferred, and a direct methanol solid polymer fuel cell is particularly preferred.
  • FIG. 1 is a schematic view showing an embodiment of a direct methanol type solid polymer fuel cell using the proton conductive electrolyte membrane of the present invention as an electrolyte membrane.
  • reference numeral 1 denotes an electrolyte membrane
  • reference numeral 2 denotes an anode electrode (fuel electrode)
  • reference numeral 3 denotes a force sword electrode (air electrode)
  • reference numeral 4 denotes an external circuit.
  • Methanol aqueous solution A is used as the fuel.
  • the overall reaction of the fuel cell is as follows:
  • the structure of the anode 2 can be a known structure.
  • it comprises a catalyst layer and a support that supports the catalyst layer from the electrolyte 1 side.
  • force sword pole 3 This structure can also be a known structure.
  • it is composed of a catalyst layer and a support that supports the catalyst layer from the electrolyte 1 side.
  • a known catalyst can be used.
  • noble metal catalysts such as platinum, palladium, ruthenium, iridium, and gold, and alloys such as platinum-ruthenium, iron-nickel, cobalt, molybdenum, and platinum are used.
  • the catalyst layer preferably contains an electron conductor (conductive material) material for the purpose of improving conductivity.
  • the electron conductor (conductive material) is not particularly limited, but an inorganic conductive material is preferably used from the viewpoint of electron conductivity and contact resistance.
  • carbon black, graphite and carbonaceous carbon materials, metals and metalloids are mentioned.
  • the carbon material a strong bon black such as channel black, thermal black, furnace black, acetylene black or the like is preferably used in view of the electron conductivity and the specific surface area.
  • an electron conductor (conductive material) carrying a catalyst such as white gold-carrying carbon is preferably used.
  • MEA membrane electrode assembly
  • a method of manufacturing a membrane electrode assembly (MEA) by joining a solid polymer electrolyte membrane and an electrode for example, platinum catalyst powder supported on carbon particles is polytetrafluoroethylene.
  • a method in which the same electrolyte solution as the electrolyte membrane is coated in advance on platinum catalyst powder a method in which a catalyst paste is applied to the electrolyte membrane, a method in which an electrode is electrolessly coated on the electrolyte membrane, and a metal complex of white metal on the electrolyte membrane.
  • a method of reducing after ion adsorption There is a method of reducing after ion adsorption.
  • a fuel flow distribution plate as a current collector in which a groove for forming a fuel flow path and an oxidant flow path is formed outside the assembly of the electrolyte membrane and electrode produced as described above.
  • a fuel cell is configured by stacking a plurality of single cells via a cooling plate or the like, with a single cell provided with an oxidant flow distribution plate (separator).
  • a plurality of single cells may be arranged on a plane (planar lamination).
  • the mixture was stirred and dispersed in an aqueous surfactant solution using a high-speed homogenizer.
  • the concentration of the dispersion was set to 20% by mass.
  • the dispersion was applied onto a polyethylene terephthalate support using a bar coater so that the film thickness after drying was 150 m, dried, and after drying, the polyethylene terephthalate support was peeled off and the temperature rising speed was 60 ° CZ. After heating up to 600 ° C over time, pre-baking at 600 ° C for 3 hours, then heating up to 1000 ° C at a heating rate of 120 ° CZ time and baking at 1000 ° C for 3 hours. 1 was made.
  • Inorganic porous membranes Nos. 2 to 4 were prepared in the same manner as the inorganic porous membrane No. 1 except that the polystyrene fine particles and the colloidal silica were changed as shown in Table 1 in the inorganic porous membrane No. 1.
  • 5022B and 5043B manufactured by Moritex Co., Ltd. were used for polystyrene fine particles having an average particle size of 220 nm and 430 nm, respectively.
  • the primary average particle size of colloidal silica is 50 nm and lOO nm
  • Snowtex YL and Snowtex MP manufactured by Nissan Chemical Co., Ltd. were used, respectively.
  • Table 1 shows the average pore diameter and porosity of inorganic porous membranes Nos. 1 to 4.
  • the porosity was calculated from the mass W per unit area S (cm 2 ), average thickness t ( ⁇ m), and density d (g / cm 3 ) by the following formula.
  • the average pore diameter was measured by a mercury intrusion method using a pore sizer 9320 manufactured by Shimadzu Corporation.
  • the proton conductive polymer (electrolyte membrane No. 1) was manufactured by filling the inorganic porous membrane No. 1 produced above with a proton conductive polymer by the following method.
  • Isopropyl alcohol: water 4: 1 in 2-acrylamido-2-methylpropanesulfonic acid, “PhosmerM” (trade name, manufactured by New Chemical Co., Ltd.), “Aqualon KH-05” (product) Name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 3-glycidoxypropyltrimethoxysilane, N, N-methylenebisacrylamide as a cross-linking agent and AIBN (2, 2'-azobis isopuchi-tolyl as a polymerization initiator) ) With a mass ratio of 100: 15: 5: 5: 1, and the inorganic porous membrane (No.
  • the inorganic porous membrane thus treated was sandwiched between polyethylene terephthalate films, heated, held at 60 ° C for 2 hours, and further maintained at 80 ° C for 2 hours to produce a proton conductive electrolyte membrane. .
  • the average thickness of the proton conductive electrolyte membrane was 150 m.
  • the average film thickness was obtained by measuring five points at any point on the thickness gauge and calculating the average.
  • the filling factor of the proton conductive polymer was 95%.
  • the compound having one or more sulfonic acid groups and one or more ethylenically unsaturated bonds in the molecule, one or more phosphate groups and one or more ethylene in the molecule Except that the compound having a polymerizable unsaturated bond, the compound represented by the general formula (1), the reactive emulsifier, and the other unsaturated compound capable of copolymerization are changed as shown in Table 2.
  • Proton conductive membranes Nos. 2 to 12 were produced in the same manner as membrane No. 1.
  • A 2-acrylamide 2-methylpropanesulfonic acid
  • B p Styrene sulphonic acid
  • Nafion 117 manufactured by DuPont was also prepared.
  • the proton-conducting electrolyte membrane was swollen in water (25 ° C), then sandwiched between two platinum electrodes, and impedance measurement was performed using a Hewlett-Packard LCR meter HP4284A to calculate proton conductivity.
  • a proton-conducting electrolyte membrane is sandwiched between the H-type cell in Fig. 2 and the amount of methanol permeating from the 2 mol ZL methanol aqueous solution in the A cell into the pure water of the B cell is measured by gas chromatography (GC —Measured in 14B). The results are shown in Table 3.
  • the proton conductive electrolyte membranes (electrolyte membranes Nos. 1 to 10) of the present invention have high proton conductivity and low methanol permeability.
  • the comparative proton-conducting electrolyte membranes (electrolyte membranes Nos. 11 and 12) have high proton conductivity like Naphion 117, but have high methanol permeability!
  • a membrane-electrode assembly was produced and evaluated by the following method using the produced proton conductive electrolyte membrane (electrolyte membrane No. 1 to 12) and naphthion 117 as a comparative sample.
  • the carbon fiber cloth substrate was subjected to water repellent treatment with polytetrafluoroethylene (PTFE), and then a carbon black dispersion containing 20% by mass of PTFE was applied and baked to produce an electrode substrate.
  • PTFE polytetrafluoroethylene
  • an anode electrode catalyst coating solution comprising a Pt—Ru-supported carbon and naphthion (DuPont) solution was applied and dried to form an anode electrode, and Pt-supported carbon and naphthion (DuPont) solution. consists force cathode electrode catalyst coating solution coated and dried to cathode - were prepared cathode electrode 0
  • MEA membrane electrode assembly
  • electrolyte membrane No. 1-12 electrolyte membrane No. 1-12
  • naphthion 117 are held by an anode electrode and a force sword electrode, respectively, and heated and pressed to form a membrane-one electrode composite (MEA) (MEA-No 1-12) and MEA-Nafion 117 were prepared.
  • MEA membrane-one electrode composite
  • This membrane-electrode assembly (MEA) was sandwiched between separators, and the fuel cell was operated by flowing 3% methanol aqueous solution on the anode side and air on the cathode side, and the current-voltage characteristics were evaluated. Table 4 shows the current density at a voltage of 0.4V.
  • the membrane-electrode assembly (MEA) (MEA-No. 1 to L0) according to the present invention is a comparative membrane-electrode assembly (MEA) (MEA-No. 11, It can be seen that the current density is larger than that of 12) and MEA-Naphion 11 7.

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Abstract

La présente invention concerne un film électrolytique conducteur de protons qui présente une conductivité de protons suffisamment élevée et une perméabilité au méthanol suffisamment faible. Ledit film électrolytique conducteur de protons comprend un film poreux inorganique et, accumulé dans les pores du film, un polymère conducteur de protons obtenu par copolymérisation d'au moins (a) un composé comportant un ou plusieurs groupes sulfo et une ou plusieurs liaisons éthyléniquement insaturées par molécule, (b) un composé comportant un ou plusieurs groupes phosphate et une ou plusieurs liaisons éthyléniquement insaturées par molécule et (c) un composé représenté par la formule générale suivante (1).
PCT/JP2005/023223 2005-01-27 2005-12-19 Film electrolytique conducteur de protons, procede pour le fabriquer et pile a combustible de type polymere solide utilisant ledit film electrolytique conducteur de protons Ceased WO2006080159A1 (fr)

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Cited By (7)

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JP2006221873A (ja) * 2005-02-08 2006-08-24 Ricoh Co Ltd 電解質膜の製造方法、電解質膜、燃料電池及び電子機器
GB2431661A (en) * 2005-10-29 2007-05-02 Basf Constr Polymers Gmbh Copolymer
JP2008130269A (ja) * 2006-11-17 2008-06-05 Nissan Motor Co Ltd プロトン伝導性コンポジット型電解質膜及びその製造方法
JP2009040805A (ja) * 2007-08-06 2009-02-26 Shin Etsu Chem Co Ltd イオン伝導性高分子物質及びその製造方法並びにイオン伝導性高分子誘導体
JP2009076399A (ja) * 2007-09-21 2009-04-09 National Univ Corp Shizuoka Univ プロトン伝導性材料、及びその製造方法
JP2012229449A (ja) * 2012-08-29 2012-11-22 Shin-Etsu Chemical Co Ltd イオン伝導性高分子物質及びその製造方法並びにイオン伝導性高分子誘導体
WO2022091912A1 (fr) * 2020-10-30 2022-05-05 東邦化学工業株式会社 Particules de résine à base de vinyle

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WO2000054351A1 (fr) * 1999-03-08 2000-09-14 Center For Advanced Science And Technology Incubation, Ltd. Membrane electrolytique pour pile a combustible et son procede de fabrication, et pile a combustible et son procede de fabrication
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JP2006221873A (ja) * 2005-02-08 2006-08-24 Ricoh Co Ltd 電解質膜の製造方法、電解質膜、燃料電池及び電子機器
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JP2009040805A (ja) * 2007-08-06 2009-02-26 Shin Etsu Chem Co Ltd イオン伝導性高分子物質及びその製造方法並びにイオン伝導性高分子誘導体
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JP2012229449A (ja) * 2012-08-29 2012-11-22 Shin-Etsu Chemical Co Ltd イオン伝導性高分子物質及びその製造方法並びにイオン伝導性高分子誘導体
WO2022091912A1 (fr) * 2020-10-30 2022-05-05 東邦化学工業株式会社 Particules de résine à base de vinyle

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