WO2007007819A1 - Solid electrolyte membrane, method and apparatus for producing the same, membrane electrode assembly and fuel cell - Google Patents

Solid electrolyte membrane, method and apparatus for producing the same, membrane electrode assembly and fuel cell Download PDF

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Publication number
WO2007007819A1
WO2007007819A1 PCT/JP2006/313918 JP2006313918W WO2007007819A1 WO 2007007819 A1 WO2007007819 A1 WO 2007007819A1 JP 2006313918 W JP2006313918 W JP 2006313918W WO 2007007819 A1 WO2007007819 A1 WO 2007007819A1
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Prior art keywords
membrane
solid electrolyte
casting
solvent
drying
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PCT/JP2006/313918
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English (en)
French (fr)
Inventor
Hiroshi Miyachi
Ryo Takeda
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Fuji Film Corporation
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Publication of WO2007007819A1 publication Critical patent/WO2007007819A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B01D71/421—Polyacrylonitrile
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0095—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
    • 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]
    • 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
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • 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
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • 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
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1093—After-treatment of the membrane other than by polymerisation mechanical, e.g. pressing, puncturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
    • B29K2081/06—PSU, i.e. polysulfones; PES, i.e. polyethersulfones or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • H—ELECTRICITY
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    • 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
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    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • 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 solid electrolyte membrane, a method and an apparatus for producing the same, membrane electrode assembly and a fuel cell using the solid electrolyte membrane, in particular, the present invention relates to a solid electrolyte membrane having proton conductivity used for the fuel cell, a method and an apparatus for producing the same, membrane electrode assembly and the fuel cell using the solid electrolyte membrane.
  • the solid electrolyte membranes are, for instance, lithium ion conductive materials and proton conductive materials.
  • the proton conductive material is formed in a membrane form.
  • the solid electrolyte in the membrane form used as a solid electrolyte layer of the battery or the cell, such as the fuel cell, and a producing method thereof are suggested in the following.
  • Japanese Patent Laid-Open Japanese Patent Laid-Open
  • Japanese Patent Laid-Open Publication No. 2002-231270 suggests a method for producing an ion exchange membrane by adding metal oxide precursor to a solution containing ion exchange resin, and then casting a liquid obtained by hydrolysis and polycondensation of the precursor.
  • Japanese Patent Laid-Open Publication No. 2004-79378 suggests a producing method of the proton conductive membrane.
  • a polymer membrane having proton conductivity is produced by a solution casting method.
  • the above polymer membrane is immersed in a water-soluble organic compound solution whose boiling point is not less than 100° C to reach equilibrium swelling, and then the water is evaporated by heating.
  • Japanese Patent Laid-Open Publication No. 2004-131530 suggests a producing method of a solid electrolyte membrane by dissolving a compound whose main component is polybenzimidazole having negative ionic group in an alcoholic solvent containing tetraalkylammonium hydroxide and whose boiling point is not less than 90 0 C.
  • the solution casting method is rejected, but the production method disclosed in this reference does not solve the problem in that the impurities contained in the material remain in the membrane.
  • the method disclosed in the above Japanese Patent Publications No. 9-320617, 2001-307752, 2002-231270 and 2004-131530 are all small-scale productions and not for large-scale manufactures.
  • the membrane forming method there are the melt extrusion method and the membrane casting method as well known. In the former method, the membrane is produced without using the solvent. However, the polymer is denatured due to heating, and impurities in the polymer material remain in the membrane.
  • the latter method requires a large sized facility including a producing apparatus of the solution which is called a dope, a solvent recovery device and the like.
  • the latter method only requires low heating temperature, and enables to remove the impurities in the polymer material.
  • a membrane with superior flatness and smoothness is produced compared to the membrane produced by the former method.
  • Japanese Patent Laid-Open Publication No. 2004-067804 suggests a method in which the solid electrolyte membrane formed of the melt-extrusion method is contacted with a reaction liquid to perform hydrolysis while transporting the solid electrolyte membrane after both side edges of the solid electrolyte membrane are held.
  • the membrane is contacted with a reaction liquid, and then both side edges of the membrane are held and stretched in the width direction while being transported. As a result, the membrane is dried without forming wrinkles and slacks in the membrane. It is also possible to continuously produce the solid electrolyte membrane on a mass-scale. However, the membrane produced in the above method does not have a sufficient mechanical strength such as durability required for the solid electrolyte membrane used for the power source for household water supply for home use, the fuel cells and the like.
  • the Japanese Patent Laid-Open Publication No. 2004-79378 cites that the solution casting method is capable of producing various solid electrolyte membranes. However, concrete method is not disclosed.
  • An object of the present invention is to solve the above problems and provide a solid electrolyte membrane with excellent proton conductivity with the constant quality, a method and apparatus for continuously producing the same on a mass-scale, and the membrane electrode assembly and the fuel cell using the solid electrolyte membrane.
  • a producing method for a solid electrolyte membrane of the present invention the following steps are performed: (A) casting a dope containing a solid electrolyte and an organic solvent from a casting die to a moving support to form a casting membrane, (B) peeling the casting membrane from the support as a wet membrane, (C) stretching the wet membrane in a width direction while transporting the wet membrane after both side edges thereof being held by membrane-holders moving along a transportation passage of said membrane, and drying the wet membrane and at least one of the casting membrane and the wet membrane is contacted with a liquid which is a poor solvent of the solid electrolyte and having lower boiling point than that of the organic solvent, and(D) drying the wet membrane after the wet membrane being released from the membrane-holders to form a solid electrolyte membrane .
  • the step (C) further includes the following steps: (Cl) keeping the holding width constant, (C2) gradually increasing the holding width, (C3) gradually reducing the holding width, and (C4) keeping the holding width constant.
  • steps (Cl) to (C4) dry air is blown onto the wet membrane for stretching and drying of the wet membrane.
  • a maximum value of the holding width in the step (C2) is B (mm)
  • the holding width at the release of the membrane from the membrane-holders after reducing the holding width is C (mm)
  • A, B and C satisfy 1 ⁇ 100 x (B-C)/A ⁇ 15.
  • the organic solvent is a mixture of a first component which is a poor solvent of the solid electrolyte, and a second component which is a good solvent of the solid electrolyte.
  • the weight ratio of the first component in the organic solvent is not less than 10% and less than 100%.
  • the first component contains alcohol having one to five carbons
  • the second component contains dimethylsulfoxide .
  • the solid electrolyte is a hydrocarbon polymer.
  • the hydrocarbon polymer is an aromatic polymer having a sulfonic acid group.
  • the aromatic polymer is a copolymer formed of structural units represented by general formulae (I), (II) and (III) shown in a chemical formula 1. [Chemical formula 1]
  • a producing apparatus for a solid electrolyte membrane is constituted of a casting membrane forming device for forming a casting membrane by casting a dope containing a solid electrolyte and an organic solvent from a casting die to a support, a peeling device for peeling the casting membrane from the support as a wet membrane, a first drying device including a plurality of membrane-holders stretching the wet membrane while moving along a transportation passage after holding both side edges of the wet membrane and a dryer for drying the wet membrane, a second drying device for drying the wet membrane after being released from the membrane-holders to form the solid electrolyte membrane, and a membrane wetting device disposed between the casting membrane forming device and the second drying device for contacting at least one of the casting membrane and the wet membrane with a liquid which is a poor solvent of the solid electrolyte and having a lower boiling point than the organic solvent.
  • the dryer has a plurality of air outlets for blowing dry air onto the wet membrane.
  • the solid electrolyte membrane of the present invention is produced by at least one of the above methods .
  • a membrane electrode assembly is constituted of the above solid electrolyte membrane, an anode electrode being adhered to one side of the solid, electrolyte membrane for generating protons from hydrogen-containing substance supplied from outside, and a cathode electrode being adhered to the other side of the solid electrolyte membrane for synthesizing water from the protons passed through the solid electrolyte membrane and a gas supplied from the outside.
  • a fuel cell of the present invention is constituted of the above membrane electrode assembly, and current collectors attached to the electrodes of the membrane electrode assembly for transmitting electrons between the anode electrode and outside and between the cathode electrode and the outside.
  • the membrane is contacted with the liquid which is a poor solvent of the above solid electrolyte and having lower boiling point than the above organic solvent. Accordingly, in the case the membrane is dried after the contact with the liquid, the organic solvent is securely evaporated together with the evaporation of the poor solvent.
  • the organic solvent for the dope a substance with a large polarity is usually used to completely dissolve the solid electrolyte. As the substance with the large polarity, there are basic substances.
  • the membrane is stretched in the width direction while transporting the membrane after the membrane side edges are held by the membrane-holders and at the same time, the membrane is dried. Accordingly, the orientation of the membrane is improved. As a result, the membrane having the excellent mechanical strength is produced. According to the present invention, it becomes possible to continually produce the membrane with a high proton conductivity and improved mechanical strength. In the case the membrane electrode assembly using the solid electrolyte membrane is used for the fuel cell, such fuel cell exerts excellent electromotive force.
  • Fig. 1 is a schematic view illustrating a dope producing apparatus
  • Fig. 2 is a schematic view illustrating a membrane producing apparatus of a first embodiment
  • Fig. 3 is a schematic view illustrating a tenter device
  • Fig. 4 is a schematic view illustrating a membrane producing apparatus of a second embodiment
  • Fig. 5 is a section view of a membrane-producing apparatus of a third embodiment
  • Fig. 6 is a section view of a membrane electrode assembly
  • Fig. 7 is an exploded section view of a fuel cell.
  • a solid electrolyte membrane of the present invention is described. Thereafter, a producing method for the solid electrolyte membrane is described.
  • a polymer having a proton donating group is used as a solid electrolyte to form a membrane. A producing method thereof will be described later.
  • the polymer having the proton donating group is not particularly limited to the following.
  • Any known polymer used as the proton conductive material having the acid residue is preferably used, for instance, polymer compounds formed of addition polymerization having the sulfonic acid group in side chains, poly(meth)acrylate having side chains of phosphoric acid groups, sulfonated poly ether ether ketone which is a sulfonated compound of poly ether ether ketone, sulfonated polybenzimidazole, sulfonated polysulfone which is a sulfonated compound of polysulfone, sulfonated compound of heat-resistant aromatic polymer compounds and so forth.
  • perfluorosulfonic acid polymer such as typically Nafion (registered trademark), sulfonated polystyrene, sulfonated polyacrylonitrile-styrene, sulfonated polyacrylonitrile butadiene-styrene and the like.
  • sulfonated compound of the heat-resistant aromatic polymer compound there are sulfonated polyimide and the like .
  • the perfluorosulfonic acid are the substances disclosed in, for instance, Japanese Patent Laid-Open Publications No. 4-366137, 6-231779 and 6-342665.
  • m is in a range of 100 to 10000 , preferably in a range of 200 to 5000, and more preferably in a range of 500 to 2000.
  • n is in a range from 0.5 to 100 , and especially preferable in a range of 5 to 13.5.
  • x is approximately equal to m
  • y is approximately equal to n.
  • sulfonated polystyrene sulfonated polyacrylonitrile styrene and sulfonated polyacrylonitrile butadiene styrene are substances disclosed in Japanese Patent Laid-Open Publication Nos. 5-174856 and. 6-111834, or the substance shown below in Chemical formula 4.
  • sulfonated compound of the heat-resistant aromatic polymer are the substances disclosed in. for instance, Japanese Patent Laid-Open Publication Nos .6-49302, 2004-10677, 2004-345997, 2005-15541, 2002-110174, 2003-100317, 2003-55457, 9-345818, 2003-257451 and 2002-105200, and PCT Publication No. WO/97/42253 (corresponding to Japanese Patent Publication of translated version No. 2000-510511).
  • the substances shown in the above Chemical formula 1, and those shown in Chemical formula 5 and Chemical formula 6 below are especially preferable. [Chemical formula 5]
  • a membrane expansion ratio by water absorption is compatible with the proton conductivity.
  • the amount of the sulfonic acid groups may be too low for forming a path for transporting the protons, that is , . the proton channel .
  • the obtained membrane may not exert the sufficient proton conductivity for a practical use .
  • n /(m+n) > 0.5 the water absorption of the membrane becomes excessively higher which result in higher membrane expansion ratio by the water absorption. As a result, the membrane is easily degraded.
  • the sulfonated reaction in the process for obtaining the above compounds is performed through the various synthesis methods disclosed in known references.
  • sulfuric acid concentrated sulfuric acid
  • fuming sulfuric acid fuming sulfuric acid
  • sulfur trioxide in a gas or liquid
  • sulfur trioxide complex amidosulfuric acid
  • chlorosulfonic acid hydrocarbons (benzene, toluene, nitrobenzene, chlorobenzene, dioxetan or the like), halogenated alkyls dichloromethane, trichloromethane, dichloroethane, tetrachloromethane, or the like) and the like are used.
  • Reaction temperature is determined in a range of -20° C to 200° C according to activity of the sulfonating agent.
  • mercapto group, disulfide group or sulfonic acid group is previously introduced to a monomer to synthesize the sulfonated compound by oxidation with an oxidizer.
  • an oxidizer hydrogen peroxide , nitric acid, bromine water, hypochlorous acid salt, hypobromite salt, potassium permanganate, chromic acid or the like are used.
  • the solvent water, acetic acid, propionic acid or the like are used.
  • the reaction temperature in the above method is determined in a range of room temperature (for instance, 25° C) to 200° C according to the activity of the oxidizer.
  • halogeno-alkyl group is previously introduced to the monomer to synthesize the sulfonated compound by substitution of sulfite acid salt, hydrogen sulfite salt or the like.
  • the solvent water, alcohol, amide, sulfoxide, sulfone or the like are used.
  • The. reaction temperature is determined in a range of the room temperature (for instance 25° C) to 200° C. It is also possible 1 Q
  • alkyl sulfonating agent in the reaction process to produce the sulfonated compounds.
  • One of the common methods is Friedel-Crafts Reaction (see Journal of Applied Polymer Science, Vol. 36, 1753-1767, 1988) using sulfone and AlCl 3 .
  • the alkyl sulfonating agent When the alkyl sulfonating agent is used to carry out the Friedel-Crafts Reaction, the following substances are usable as the solvent: hydrocarbon (benzene, toluene, nitrobenzene, acetophenon, chlorobenzen, trichlorobenzene or the like), alkyl halide (dichloromethane, trichloromethane, dichloroethane, tetrachloromethane, trichloroethane, tetrachloroethane or the like) or the like.
  • the reaction temperature is determined in a range of the room temperature to 200 0 C. It is also possible to use the mixture of two or more solvents .
  • a dope is prepared containing a polymer whose X in the chemical formula 1 is cation species other than hydrogen atom H (hereinafter referred to as a precursor) .
  • the dope is cast onto a support and then peeled off as a membrane containing the precursor (hereinafter referred to as a precursor membrane) .
  • the cation species is an atom or an atomic group which generates ⁇ ation(s) at the time of ionization.
  • the cation species may have a valence of one or more.
  • alkali-metal cation, alkali earth metal cation and ammonium cation are preferable in addition to proton, and calcium ion, barium ion. quaternary ammonium ion, lithium ion, sodium ion, potassium ion are more preferable.
  • the membrane obtains the function as the solid electrolyte even if the substitution of the hydrogen atom H for the cation species X in the chemical formula 1 is not performed. However, the proton conductivity of the membrane increases as the percentage of the substitution of the hydrogen atom H for X (the cation species) increases. For that reason, it is especially preferable that X is the hydrogen atom H.
  • the proton conductivity is preferably not less than 0.005S/cm and more preferably not less than 0.01S/cm at the temperature of, for instance, 25° C, and the relative humidity of , for instance, 70%.
  • the proton conductivity after immersing the membrane in 50% aqueous methanol solution for one day at the temperature of 18° C is preferably not less than 0.003S/cm, and more preferably not less than 0.008S/cm.
  • Methanol diffusivity is preferably not more than 4 x lO "7 cm 2 /sec, and especially preferably not more than 2 x 10 "7 cm 2 /se ⁇ .
  • elastic modulus is preferably not less than 10MPa, and more preferably not less than 20MPa. Measuring methods of the elastic modulus are disclosed in a paragraph [0138] of Japanese Patent Laid-Open Publication No. 2005-104148. The above preferable values are obtained by using a tensile testing device produced by Toyo Baldwin Co. Ltd. If other measuring method and/or other tensile testing device are used, correlation between the obtained value and the value obtained by using the above tensile testing device should be previously calculated.
  • a percentage of change in each of weight, ion exchange capacity, and methanol diffusivity is preferably not more than 20%, and more preferably not more than 15% . Further, in a test with time in hydrogen peroxide, a percentage of change in each of weight, ion exchange capacity, methanol diffusivity is preferably not more than 20%, and more preferably not more than 10%.
  • the volume swelling ratio of the membrane in 50% methanol at the constant temperature is preferably not more than 10% and more preferably not more than 5%.
  • the membrane with stable water absorption ratio and stable moisture content is preferable. It is preferable ' that the membrane has extremely low solubility in the alcohols, water, or mixture of alcohol and water to the extent that it is practically negligible. It is also preferable that the decrease of the membrane weight and changes in shapes and conditions of the membrane when the membrane is immersed in the above liquid is extremely small to the extent that it is practically negligible .
  • the ion conductivity property of the solid electrolyte membrane is represented by an index which is a ratio of the ion conductivity to the methanol transmission coefficient. The higher the index in a certain direction, the higher the ion conductive property becomes in such direction.
  • the ion conductivity increases proportional to the thickness while the methanol permeability increases inversely proportional thereto . Accordingly, the ion conductive property of the solid electrolyte membrane is controlled by changing the thickness.
  • the anode is provided on one side of the solid electrolyte membrane and the cathode is provided on the other side of the Ib
  • the index in the membrane thickness direction is larger than that in other directions .
  • the thickness of the solid electrolyte membrane is preferably in a range of lO ⁇ i and 300 ⁇ m. If, for instance, both the ion conductivity and the methanol diffusion coefficient are high in the solid electrolyte, it is especially preferable to produce the membrane with a thickness of 50 ⁇ m - 200 ⁇ m. If, for instance, both the ion conductivity and the methanol diffusion coefficient are low in the solid electrolyte, it is especially preferable to produce the membrane with a thickness of 20 ⁇ m - lOO ⁇ m.
  • Heat resistant temperature is preferably not less than 200 0 C, more preferably not less than 250 0 C and especially preferably not less than 300 0 C.
  • the heat resistant temperature means the temperature at which a decrease in the membrane weight reaches 5% when the heat is increased at the measure of 1° C/min. The decrease in the membrane weight does not include an amount of moisture and the like evaporated from the membrane.
  • the maximum power density thereof is preferably not less than lOmW/cm 2 .
  • a solution suitable for the membrane production is produced, and accordingly, the solid electrolyte membrane suitable for producing the fuel cell is produced.
  • the solution suitable for the membrane production is, for instance, a solution whose viscosity is relatively low, and from which foreign matters are easily removed through filtration.
  • the obtained solution is referred to as a dope in the following descriptions.
  • the solvent for the dope an organic solvent in which polymer, that is, the solid electrolyte is dissolved is used.
  • aromatic hydrocarbon for instance, benzene, toluene and the like
  • halogenated hydrocarbon for instance, dichloromethane, chlorobenzene and the like
  • alcohol for instance, methanol, ethanol, n-propanol, n-butanol, diethylene glycol and the like
  • ketone for instance, acetone, methyl ethyl ketone, and the like
  • ester for instance, methyl acetate, ethyl acetate, propyl acetate and the like
  • ether for instance, tetrahydrofuran, ethylene glycol monomethyl ether
  • compounds containing nitrogen N-methylpyrrolidone, N, N-dimethylformamide (DMF), N, N' -dimethylacetamide (DMAc) and the like
  • dimethyl surfoxide DMSO
  • the solvent of the dope it is also possible to use a mixture in which plural substances are mixed.
  • the mixture it is preferable to mix the good solvent and the poor solvent of the solid electrolyte.
  • the proton substitution is carried out in a production of the solid electrolyte membrane having the structure shown in the Chemical formula 1, it is preferable to use a good solvent and a poor solvent of the precursor of the solid membrane.
  • the solvent and the solid electrolyte are mixed suchothat the solid electrolyte constitutes 5 wt. % of the whole weight. Whether the solvent used is the poor solvent or the good solvent of the solid electrolyte is determined by the amount of the insoluble residues.
  • the good solvent of the solid electrolyte in which the solid electrolyte is dissolved has a relatively high boiling point compared to the commonly used compounds.
  • the poor solvent has a relatively low boiling points compared to the commonly used compounds. Accordingly, by mixing the poor solvent to the good solvent, the boiling point of the mixture in which the solid electrolyte is dissolved is lowered. As a result, efficiency and Io
  • weight ratio of the poor solvent is preferable, concretely, not less than 10% and less than 100% is preferable, and more preferably a ratio of (weight of the good solvent) : (weight of the poor solvent) is in a range of 90:10 to 10:90.
  • a ratio of (weight of the good solvent) : (weight of the poor solvent) is in a range of 90:10 to 10:90.
  • the good solvent DMF, DMAc, DMSO and NMP are preferable.
  • DMSO is especially preferable in terms of safety and relatively low boiling point.
  • the poor solvent lower alcohol having 1 to 5 carbons, methyl acetate and acetone are preferable.
  • the lower alcohol having 1 to 3 carbons are more preferable. If the DMSO is used as the good solvent, methyl alcohol is especially preferable in terms of excellent solubility in the DMSO.
  • additives are added to the dope.
  • antioxidant agents As the additives, antioxidant agents, fibers, fine particles, water absorbing agents, plasti ⁇ izers, solubilizers and the like are used.
  • a ratio of the additives is preferably in a range of 1 wt . % to 30 wt . % when the whole solid component in the dope is 100 wt . % .
  • the ratio and the sorts of the additives should not adversely affect the proton conductivity.
  • the additives will be described in the following.
  • antioxidant agent for instance, compounds such as hindered phenols , monovalent or divalent sulfurs , trivalent phosphates, benzophenones, bonzotriazoles, hindered amines. cyanoacrylates , sallicylates and oxalic acid anillides are preferably used.
  • compounds disclosed in Japanese Patent Laid-Open Publications No. 8-53614, 10-101873, 11-114430 and 2003-151346 are preferably used.
  • fibers for instance, perfluorocarbon fibers, cellulose fibers, glass fibers and polyethylene fibers are preferably used. In specific, the fibers disclosed in Japanese Patent Laid-Open Publications No.
  • 10-312815, 2000-231938, 2001-307545, 2003-317748, 2004-63430 and 2004-107461 are used.
  • the fine particles for instance, titanium oxide, zirconium oxide and the like are preferably used.
  • the fine particles disclosed in Japanese Patent Laid-Open Publications No. 2003-178777 and 2004-217931 are preferably used.
  • the hydrophilic substances for instance, cross-linked polyacrylate acid salt, starch-acrylate salt, poval (polyvinyl alcohol), polyacrylonitrile, carboxymethylcellulose, polyvinylpyrrolidone , polyglycoldialkylether, polyglycoldialkylesther, synthetic zeolite, titania gel, zirconia gel, and yttria gel are preferably used.
  • the water absorbers disclosed in Japanese Patent Laid-Open Publications No. 7-135003, 8-20716 and 9-351857 are preferably used.
  • plasticizer for instance, phosphoric acid ester compound, chlorinated paraffin, alkylnaphthalene compound, sulfone alkylamide compound, oligo ether, and aromatic nitrile are preferably used.
  • plasticizers disclosed in Japanese Patent Laid-Open Publications No. 2003-288916 and 2003-317539 are preferably used.
  • solubilizers substances whose boiling points or sublimation points are not less than 250° C are preferable, and those not less than 300° C are more preferable.
  • polymers to the dope for following objectives: ( 1 ) to enhance the mechanical strength and (2) to increase the acid concentration in the membrane.
  • a polymer whose molecular weight is approximately in a range of 10000 to 1000000 and soluble to the solid electrolyte is suitable to achieve the above objective (1).
  • perfluoropolymer, polystyrene, polyethyreneglycol, polyoxetane, polyether ketone, polyether sulfone, and the polymers containing two or more structural repeating units of the above polymers are preferable.
  • the weight ratio of the above polymer(s) with respect to the whole weight of the dope is in a range of 1 wt . % and 30 wt . % . It is also possible to improve the solubility of the above polymer in the solid electrolyte by adding the solubilizer.
  • the solubilizer the substance with the boiling point or the sublimation point of not less than 250° C is preferable, and that not less than 300° G is more preferable.
  • a polymer having proton acid segment and the like is preferable to achieve the above objective (2) .
  • perfluorosulfone acid polymer such as Nafion (registered trademark)
  • sulfonated polyether ether ketone having phosphoric acid in the side chain sulfonated heat-resistant aromatic polymer compounds such as sulfonated poly ether sulfone, sulfonated polysulfone, sulfonated polybenzimidazole and the like are used.
  • an active metal catalyst to the dope for promoting redox reaction of the anode fuel and ⁇
  • Active metal catalyst is not particularly limited as long as it functions as the catalyst for the electrodes. However, platinum or platinum based alloy is especially suitable .
  • Fig. 1 illustrates a dope producing apparatus 10.
  • the dope producing apparatus 10 is constituted of a solvent tank 11, a hopper 12, an additive tank 15, a mixing tank 16, a heating device 18, a temperature controlling device 21, a filtration device 22, a flash device 26, and a filtration device 27.
  • the solvent tank 11 stores the solvent.
  • the hopper 12 supplies a solid electrolyte.
  • the additive tank 15 stores the additive.
  • the mixing tank 17 mixes the solvent, the solid electrolyte and the additive to form a liquid mixture 16.
  • the heating device 18 heats the liquid mixture 16.
  • the temperature controlling device 21 controls the temperature of the heated liquid mixture 16.
  • the filtration device 22 filters the liquid mixture 16.
  • the flash device 26 controls the concentration of the dope 24. Then the filtration device 27 filters the dope 24.
  • the dope producing apparatus 10 further includes a recovery device 28 and a refining device 29.
  • the recovery device 28 recovers the solvent.
  • the refining device 29 refines the recovered solvent.
  • the dope producing apparatus 10 is connected to a membrane producing apparatus 33 via a stock tank 32. Valves 36-38 for controlling a liquid feeding amount and pumps 41, 42 for feeding the liquid are.provided in the dope producing apparatus 10. The positions and the number of the valves and the pumps are properly changed.
  • the dope 24 is produced in the following method when the dope producing apparatus 10 is used. First, the valve 37 is opened to feed a solvent from the solvent tank 11 to the mixing tank 17.
  • the solid electrolyte in the hopper 12 is fed to the mixing tank 17.
  • the solid electrolyte may be continuously fed to the mixing tank 17 through a supplying device which continuously measures and supplies the solid electrolyte, or intermittently fed to the mixing tank 17 through a supplying device which measures and supplies the solid electrolyte by a predetermined amount. Further, the valve 36 is adjusted to feed a necessary amount of additive, solution from the additive tank 15 to the mixing tank 17.
  • the additive can be fed to the mixing tank 17 in the liquid form.
  • the additive in the case the additive is solid, it is possible to use the hopper 12 to feed the additive to the mixing tank 17.
  • To add several additives it is possible to dissolve several additives in a solution and put the solution in the additive tank 15. It is also possible to use plural additive tanks .
  • Each of the additive tanks is filled with the solution containing a different additive.
  • Each solution may be separately fed to the mixing tank 17 through a pipe independent from each other.
  • the additive solution is used, as the solvent for the additive solution, it is preferable to use the same solvent used for the preparation of the dope.
  • the solvent, the solid electrolyte and the additive are put into the mixing tank 17 in this order; however, the order is not restricted. For instance, a preferable amount of the solvent is fed to the mixing tank 17 after feeding the solid electrolyte to the mixing tank 17. Further, it is not necessary to mix the additive in the mixing tank 13 together with the solid electrolyte and the solvent.
  • the additive may be mixed to the mixture of the solid electrolyte and the solvent by using an inline-mixing method in a later process.
  • a jacket 46, a first stirrer 48 rotated by a motor 47 and a second stirrer 52 rotated by a motor 51 are preferably attached to the mixing tank 17.
  • the jacket 46 wraps around the mixing tank 17 to supply a heat transfer medium in a space between the mixing tank 17 and the jacket 46.
  • the temperature of the mixing tank 17 is controlled by the heat transfer medium flowing in the space between the tank 17 and the jacket 46.
  • a preferable temperature range of the mixing tank 17 is from -1O 0 C to 55° C.
  • the liquid mixture 16, in which the solid electrolyte is swelled in the solvent is obtained by properly selecting and rotating the first and second stirrers 48, 52. It is preferable that the first stirrer 48 has an anchor blade, and the second stirrer 52 has an eccentric stirrer of a dissolver type.
  • the liquid mixture 16 is transported to the heating device 18 through the pump 41. It is preferable that a pipe through which the liquid mixture 16 passes in the heating device 18 is provided with the jacket .
  • the heat transfer medium passes through a space between the pipe and the jacket.
  • the heating device 18 preferably has a pressurizing section (not shown) to apply pressure to the liquid mixture 16.
  • the method for dissolving the solid electrolyte in the solvent by heating is referred to as a heat dissolution method.
  • the liquid mixture 16 is preferably heated to reach the temperature in a range of 6O 0 C to 25O 0 C.
  • a cooling- dissolution method is possibly used for dissolving the solid electrolyte in the solvent.
  • the liquid mixture 16 is preferably cooled in a range of -100° C to -10° C. It becomes possible to sufficiently dissolve the solid electrolyte contained in the liquid mixture 16 in the solvent by properly selecting one of the heat-dissolving method and the cooling-dissolving method.
  • the temperature of the liquid mixture 16 is adjusted by the temperature control device 21 to reach the room temperature. Thereafter, the liquid mixture 16 is filtered through the filtration device 22 to remove, the foreign matters such as the impurities and the agglomeration.
  • the liquid mixture 16 is referred to as the dope 24.
  • An average pore diameter of the filter of the filtration device 22 is preferably 50 ⁇ m or less and more preferably 10 ⁇ m or less.
  • the dope 24 is transported to the, stock tank 32 through the valve 38 and temporarily stored, and then used for the membrane production.
  • the dope 24 filtered through the filtration device 22 is transported to the flash device 26 through the valve 38, and a part of the solvent contained in the dope 24 is evaporated to concentrate the dope 24.
  • the concentrated dope 24 is transported from the flash device 26 to the filtration device 27 through the pump 42.
  • the temperature of the dope 24 is preferably from O 0 C to 200 0 C.
  • the impurities of the dope 24 are removed through the filtration device 27. Thereafter, the dope 24 is transported to and temporarily stored in the stock tank 32, and then used for the membrane production.
  • the foams may be formed in the concentrated dope 24. It is preferable to perform processing to remove the foams prior to transporting the concentrated dope 24 to the filtration device 27. It is possible to apply known methods, for instance, an ultrasonic irradiation method in which the ultrasound is irradiated to the dope 24 for removing the foams .
  • the solvent vapor generated by the flash evaporation in the flash device 26 is condensed to liquid and recovered by the recovery device 28 having the condenser (not shown) .
  • the recovered solvent is refined as the solvent for the dope production in the refining device 29 and reused. Such recovery and refining are advantageous to reduce production cost and also prevent adversely affecting human health and environment by virtue of the closed system.
  • the dope 24 whose concentration of the solid electrolyte or that of the precursor is in a range of not less than 5 wt.% and not moire than 50 wt.% is produced.
  • the concentration of the solid electrolyte or that of the precursor is more preferably in a range of not less than 10 wt.% and not more than 40 wt.%.
  • the concentration of the additive is preferably in a range of not less than 1 wt . % and not more than 30 wt.% when the whole solids contained in the dope 24 is considered to be 100 wt.%.
  • Fig. 2 is a schematic view illustrating a membrane producing apparatus 33.
  • the present invention is not limited to the following methods and apparatuses for producing the solid electrolyte membrane.
  • the membrane producing apparatus 33 is provided with a filtration device 61, a casting chamber 63, a tenter device 64, an edge slitting device 67 , a first liquid bath 65 , a second liquid bath 66, a drying chamber 69, a cooling chamber 71, a neutralization device 72 , a knurling roller pair 73 and a winding device 76.
  • the filtration device 61 removes the impurities from the dope 24 transported from the stock tank 32.
  • the dope 24 is cast to form a solid electrolyte membrane (hereinafter referred to as a membrane) 62.
  • the tenter device 64 dries the membrane 62 while holding the both side edges of the membrane 62.
  • the edge slitting device 67 cuts off the side edges of the membrane 62.
  • the membrane 62 is immersed in the first bath 65 and the second bath 66.
  • the drying chamber 69 the membrane 62 is bridged across plural rollers 68 and dried while the membrane 62 is being transported by the rollers 68.
  • the membrane 62 is cooled.
  • the neutralization device 72 reduces the charged voltage of the membrane 62.
  • the nurling roller pair 73 embosses the side edges of the membrane 62.
  • the winding device 76 winds the membrane 62.
  • a stirrer 78 rotated by a motor 77 is provided in the ' stock tank 32. By using the stirrer 78 , precipitation and agglomeration of the solids in the dope 24 are prevented.
  • the stock tank 32 is connected to the filtration device 61 through a pump 80.
  • the casting chamber 63 is provided with a casting die 81 for casting the dope 24, and a belt 82 which is a support being transported.
  • a precipitation hardened stainless steel is preferable for the material of the casting die 81.
  • the material preferably has a coefficient of thermal expansion at most 2xlO "5 (°C "1 J. Further, the material with the almost same anti-corrosion properties as SUS316 in examination of corrosion in electrolyte solution can also be used. Further, the material has the anti-corrosion properties which do not form pitting (holes) on the gas-liquid interface after having been dipped in a liquid mixture of dichloromethane , methanol and water for three months.
  • the casting die 81 it is preferable to manufacture the casting die 81 by grinding the material which passed more than a month after casting. Thereby, the dope 24 flows inside the casting die 81 uniformly. Accordingly, streaks and the like in a casting membrane 24a are prevented, as will be described later. It is preferable that the finish precision of a contacting surface of the casting die 81 to the dope 24 is l ⁇ mor less of the surface roughness and the straightness is 1 ⁇ m/m or less in any direction . Clearance of the slit of the casting die 81 is automatically controlled in the range of 0.5mm to 3.5mm.
  • a portion of the lip end of the casting die 81 contacting the dope is processed so as to have a constant chamfered radius R at 50 ⁇ m or less throughout the width of the casting die 81.
  • the casting die 81 is of a coat-hanger type.
  • a width of the casting die 81 is not limited. However, the width of the casting die 81 is preferably in the range between 1.1 times and 2.0 times larger than a width of the membrane as an end product. Further, it is preferable to install a temperature controlling device 21 to the casting die 81 for maintaining a predetermined temperature of the dope 24 during the production of the membrane. Further, the casting die 81 is preferably provided with bolts (heat bolts) at predetermined intervals in the width direction of the casting die 81 for adjusting the thickness of the membrane, and an automatic thickness control mechanism which adjusts clearance of the slit by using the heat bolts. In the membrane production process, it is preferable to set a profile according to the flow volume of the pump 80 based on the previously set program. To accurately control the amount of the dope to be transported, the pump 80 is preferably a high-precision gear pump. Further, in the o
  • the membrane producing apparatus 33 it is also possible to carry out a feedback control based on an adjustment program according to a profile of a thickness gauge, for instance, an infrared thickness gauge (not shown) .
  • the casting die 81 whose slit opening of the lip end is adjustable within a range of ⁇ 50 ⁇ m is preferably used so as to maintain a difference in the thickness between two arbitrary positions on the membrane 62 within I-Mm except for the side edges of the membrane 62 as the end product.
  • lip ends of the casting die 81 are provided with a hardened layer.
  • Methods for forming the hardened layer are not particularly limited. For instance, there are methods such as ceramic coating, hard chrome plating, and nitriding treatment. If the ceramic is used as the hardened layer, the ceramic which is grindable but not friable, with a lower porosity and the good corrosion resistance is preferred. The ceramic without affinity for and adherence to the casting die 30 is preferable.
  • tungsten carbide, Al 2 O 3 , TiN, Cr 2 O 3 and the like can be used, and especially tungsten carbide (WC) is preferable.
  • a WC coating is performed in a thermal spraying method.
  • the dope discharged to the lip end of the casting die 81 is partially dried and becomes solid.
  • a solvent supplying device (not shown) for supplying the solvent to the lip end is preferably disposed in the proximity of the lip end.
  • the solvent is preferably supplied in a peripheral area of a three-phase contact line on which the lip ends contacts with the casting bead and the outside air. It is preferable to supply the solvent in the range from 0.1 mL/min to 1.0 mL/min to each of the bead edges so as to prevent the foreign matters such as impurities precipitated from the dope or those outside the dope from being mixed in the casting membrane 24a. It is preferable to use a pump ⁇
  • the belt 82 below the casting die 81 is bridged across the rollers 85, 86, and is continuously transported by the driving and rotation of at least one of the rollers 85, 86.
  • the width of the belt 82 is not particularly limited. However, the width is preferably in a range of 1.1 times to 2.0 times larger than the casting width of the dope 24. Further, the length of the belt 82 is preferably 20m-200m. The thickness of the belt 82 is preferably 0.5mm to 2.5mm. Further the belt 82 is preferably polished such that the surface roughness is 0.OS 1 Um or less.
  • Material of the belt 82 is not particularly limited. However, it is preferable to use a plastic film which is insoluble to the organic solvent in the dope 24.
  • the material of the plastic film is preferably nonwoven plastic fabric made of polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, nylon 6 film, nylon 6, 6 film, polypropylene film, polycarbonate film, polyimide film and the like.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • nylon 6 film nylon 6, 6 film, polypropylene film, polycarbonate film, polyimide film and the like.
  • the belt 82 of a long length is preferable. It is preferable that the belt 82 has chemical stability against the solvent used. It is also preferable that the belt 82 is heat-resistant to endure the temperature of the membrane production. Note that it is also possible to use a stainless support with the long length.
  • a heat transfer medium circulating device 87 is attached to the rollers 85 and 86.
  • a passage (not shown) for the heat transfer medium is formed in each of the rollers 85 and 86.
  • the temperature of the rollers 85 and 86 are kept at the predetermined value by passing the heat transfer medium kept at the predetermined temperature through the passages.
  • the surface temperature of the belt 82 is properly set according to the type ⁇
  • the rollers 85, 86 and the belt 82 it is also possible to use a casting drum (not shown) as the support.
  • the casting rotates with a high precision such that the variation in the rotation speed is 0.2% or less .
  • the polishing is made such that a surface roughness is O.Ol ⁇ m or less.
  • the surface of the casting is hard chrome-plated which offers sufficient corrosion resistance and hardness. It is preferable to minimize the surface defect of the casting drum, the belt 82 and the rotation rollers 85, 86.
  • the number of pin holes whose diameter is 30 ⁇ m or more is preferably zero.
  • the number of pinholes whose diameter is not less than 10 ⁇ m and less than 30 ⁇ m is preferably 1 or less per Im 2 .
  • the number of pinholes whose diameter is less than 10 ⁇ m is preferably 2 or less per Im 2 .
  • a decompression chamber 90 is preferably provided in the proximity of the casting die 81 for adjusting the pressure in the upstream area from the casting bead in the support moving direction.
  • the casting bead is formed between the casting die 81 and the belt 82.
  • air blowers 91, 92 and 93 and an air shielding plate 94 are provided in the proximity of the belt 82.
  • the air blowers 91 to 93 blow air onto the casting membrane 24a to evaporate the solvent.
  • the air shielding plate 94 prevents the air which may damage the surface of the casting membrane 62 from blowing onto the casting membrane 24a.
  • a temperature controlling device 97 and a condenser 98 are provided in the casting chamber 63 .
  • the temperature controlling device 97 keeps the temperature inside the casting chamber 63 at the predetermined value.
  • the condenser 98 condenses and ⁇
  • a recovery device 99 is provided outside the casting chamber 63.
  • the recovery device 99 recovers the condensed and liquefied organic solvent .
  • a transporting section 101 is provided in the downstream from the casting chamber 63.
  • an air blower 102 is provided for blowing dry air onto the membrane 62.
  • the membrane 62 passed through the transporting section 101 is transported to the tenter device 64 in which the membrane 62 is stretched in the width direction while both side edges are held by membrane holding members such as clips 64a or pins.
  • the dry air is introduced to the tenter device 64 to dry the membrane 62. Note that it is preferable to separate inside the tenter device 64 into different temperature zones to adjust the drying conditions.
  • the membrane 62 is transported to the edge slitting device 67.
  • a crusher 103 is provided for crushing the side edges cut off from the membrane 62 into chips.
  • the tenter device 64 will be described in detail later.
  • the membrane 62 whose side edges are cut off and removed is transported to the first and second liquid baths 65 and 66 through guide rollers 65b, 65c, 66b and 66c.
  • a first liquid 65a is put in the first liquid bath 65.
  • As the first liquid 65a a liquid soluble to and having a lower boiling point than the solvent of the dope 24 and in which the polymer is insoluble is used. It is possible to use a liquid mixture containing liquids other than the above liquid. It is preferable that the temperature of the first liquid 65a in the first liquid bath 65 is adjustable in a range of 10° C and 150 0 C.
  • a second liquid 66a is put in the second liquid bath 66.
  • the second liquid 66a a similar liquid to the first liquid 65a is used. It is also possible to use the liquid mixture in the same manner as the first liquid 65a.
  • the second liquid 66a it is preferable to use the liquid whose boiling point is lower than that of the first liquid 65a. It is preferable that the temperature of the second liquid 66a in the second liquid bath 66 is adjustable in a range of 10° C and 150 0 C.
  • an absorbing device 106 is provided in the drying chamber 69. The absorbing device 106 absorbs and recovers the solvent vapor evaporated from the membrane 62.
  • a cooling chamber 71 is provided downstream from the drying chamber 69.
  • the neutralization device 72 is a neutralization bar or the like which controls the charged voltage of the membrane 62 in a predetermined range (for instance from -3kV to +3kV) .
  • the neutralization device 72 is disposed downstream from the cooling device 71 as an example.
  • the position of the neutralization device 72 is not limited to that illustrated in Fig. 2.
  • the knurling roller pair 73 embosses the both side edges of the membrane 62.
  • Inside the winding device 76 a winding roll 107 and a press roller 108 are provided inside the winding device 76.
  • the winding roll 107 winds up the membrane 62.
  • the press roller 108 controls the tension of the membrane 62 at the time of winding.
  • FIG. 3 is a schematic view of the tenter device 64 used in this embodiment of the present invention.
  • the tenter device 64 is constituted of clips 64, air blower 64b, a pair of an endless chain 160 on which a plurality of clips 64a are attached with predetermined pitches, rails 162 for guiding the chains 160, chain sprockets 164 across which the chain is bridged and a driving section 165 which drives the chain sprockets 164.
  • the membrane is transported to the tenter device 64 through the transporting section 101.
  • both side edges of the membrane is held by the clips 64a.
  • the chains 160 move along the rails 162 such that the membrane 62 is stretched in the width direction in accordance with the distance between the rails 162.
  • the membrane is stretched in the width direction.
  • the drying of the membrane 62 is promoted through the tenter device 64.
  • the membrane is 62 is released from the clips 64a.
  • the driving sections 165 are installed at one of the entrance 170 and the exit 171 to drive the chain sprockets 164 facing each other.
  • the installation positions are not limited to the above.
  • the distance between rails 162 are constant.
  • a stretching section which is a second section in the tenter device 64, the distance between the rails 162 are gradually increased so as to gradually increase the clip width A at the entrance 173 of the stretching section as the membrane 62 proceeds in the membrane transporting direction. Thereby, the membrane 62 is stretched in the width direction. Since the entrance 173 of the stretch section is the same as an exit of the introducing section, the same numeral 173 is assigned thereto .
  • a stretch-relaxation section which is a third section in the tenter device 64
  • the distance between the rails 162 are decreased so as to decrease the clip width B at the entrance of the stretch-relaxation section, as the membrane 62 proceeds to the exit of 175 of the stretch-relaxation section.
  • stress relaxation acts to the membrane 62 so that the drying of the membrane 62 is promoted while preventing the contraction.
  • the entrance 174 of the stretch-relaxation section is the same as an exit of the stretching section, the same numeral 174 ⁇
  • the membrane 62 is transported while keeping the width size of the membrane 62 at an exit 175 of the stretch-relaxation section. Since an entrance 175 of the holding section is the same as the exit 175 of the stretching section, the same numeral 175 is assigned thereto.
  • the clip width A (mm) of the membrane 62 in the introducing section, a maximum clip width B (mm) in the stretching section, and a width C (mm) of the membrane 62 when the membrane 62 is released from the clips 64a satisfy 1 ⁇ 100 x (B-C) /A ⁇ 15.
  • changes in the shape and condition of the membrane 62, such as wrinkles or slacks are prevented.
  • the membrane 62 is contracted by evaporating the solvent from the membrane 62 in a state that the volatile solvent amount is very high in the membrane 62. Accordingly, the shapes and conditions of the membrane 62 changes to a large extent .
  • the clip widths in the above A, B and C are defined as a distance between opposite clips 64a with respect to the transportation passage when the clips 64a hold the membrane 62.
  • the dope 24 is kept uniform by the rotation of the stirrer 78. It is possible to add various additives to the dope 24 while the dope 24 is being stirred. At this time, it is also possible to mix various additives to the dope 24.
  • the dope 24 is fed to the filtration device 61 through a pump 80 and filtered. Thereby, foreign matters having the particle size larger than the predetermined value and those in gel-form are removed. Then the dope 24 is cast onto the belt 82 from the casting die 81. It is preferable that the rollers 85 and 86 are driven so as to adjust the tension of the belt 82 in a range of 10 3 N/m and 10 6 N/m.
  • the casting amount of the dope 24 is determined according to the concentration of the dope 24 and the required thickness of the membrane product.
  • speed fluctuation of the belt 82 is 0.5% or less, and meandering thereof caused in a width direction while the belt 82 makes one rotation is 1.5mm or less.
  • a detector not shown
  • a position controller not shown
  • the detector detects the positions of both sides of the belt 82.
  • the position controller adjusts the position of the belt 82 according to a measurement value of the detector.
  • vertical positional fluctuation caused in association with the rotation of the belt 82 is adjusted to be 200 Mm or less.
  • the temperature in the casting chamber 63 is adjusted within a range of -10 0 C and 57° C by the temperature controlling device 97.
  • the solvent vapor in the casting chamber 63 is collected by the recovery device 99 and is recycled and reused as the dope for preparing the solvent .
  • the humidity inside the casting chamber 63 low as much as possible by absorbing the solvent vapor and so forth as above.
  • the humidity is preferably 50% RH or less. If the humidity is high inside the casting chamber 63, the casting o
  • the membrane absorbs the moisture in the air which may cause the separation of the layers of the membrane and an increase in a percentage of voids.
  • the humidity is 20% or less. In this embodiment, the humidity is 10% or less.
  • the casting bead is formed between the casting die 81 and the belt 82, and the casting membrane 24a is formed on the belt 82.
  • the upstream area from the casting bead in the transporting direction of the casting die 81 is decompressed by the decompression chamber 90 to achieve a predetermined pressure value.
  • the upstream area from the casting bead is decompressed within a range of -2500Pa and -lOPa relative to the downstream area from the casting bead.
  • a jacket (not shown) is attached to the decompression chamber 90 to maintain the inside temperature at a predetermined value.
  • a suction unit (not shown) to an edge of the casting die 81 in order to keep a desired shape of the casting bead.
  • a preferable range of air volume aspirated in the edge portion is lL/min to lOOL/min.
  • the casting membrane 24a After the casting membrane 24a has possessed a self-supporting property, the casting membrane 24a is peeled off as the membrane 62 from the belt 82 while being supported by a peel roller 109. After that, the membrane 62 containing the solvent is carried along the transporting section 101 supported by the many rollers to the tenter device 64. In the transporting section 101, it is possible to give a draw tension to the membrane 62 by increasing a rotation speed of the downstream roller relative to that of the upstream roller. In the transporting section 101, dry air of a desired temperature is sent from the air blower 102 to the proximity of or directly to the membrane ⁇
  • the temperature of the dry air is in a range of 20° C to 250 0 C.
  • the membrane 62 is transported to the tenter device 64.
  • the drying of the membrane 62 is promoted by supplying the dry air from the air blower 64b provided in the tenter device 64 while the membrane 62 is transported inside the tenter device 64 with both side edges of the membrane 62 held by the clips 64a.
  • the distance between opposing rails of tenter device 64 used in this embodiment is adjusted so as to change the distance of the opposing clips 64a to change the width of the film 62 while the film is being transported.
  • a holding width of the film 62 is held at a constant value at first. Next, the holding width is increased and then reduced. Lastly, the holding width is held at the constant value.
  • the membrane 62 In general, in drying the membrane 62 in which a large amount of the solvent is contained, the total amount of the solvent vapor from the membrane 62 increases as the drying process proceeds. Accordingly, the membrane 62 is likely to contract in the width direction. This tendency becomes more apparent as the drying temperature increases. However, the planarity of the membrane is degraded since the contraction causes changes in the shape and condition of the membrane 62.
  • the clip width of the membrane 62 is gradually adjusted by establishing the stretch-relaxation process. Accordingly, the contraction of the membrane 62 in the width direction is prevented so that the solid electrolyte membrane with the excellent planarity is produced.
  • the tension applied to the membrane 62 is adjusted, it becomes possible to adjust the orientation by controlling the stretching and contraction of the membrane 62 in the width direction. As a result, it becomes possible to impart excellent mechanical OO
  • the air blower 64b having a plurality of air outlets is used so as to directly blow the dry air of the predetermined temperature to the membrane 62. If the drying temperature varies while the width of the membrane 62 is changed, such changes may damage the shape and condition of the membrane to a great extent. For that reason, the temperature of the dry air is preferably kept constant while the clip width 64a of the clips is being changed.
  • the membrane After being peeled off from the support, the membrane contains a large amount of the solvent. To dry such membrane, it is preferable to provide plural drying processes of different temperatures so as to gradually dry the membrane . To prevent the changes in the shape and condition of the membrane by abruptly evaporating the solvent, it is preferable that the temperature for drying the peeled membrane is gradually increased by three to four stages in a range of 4O 0 C and 140 0 C. For instance, in case the dryer which supplies the dry air is used, the temperature of the dry air is adjusted to satisfy the above conditions . The dryer is included in the tenter device.
  • membrane-holders such as the clips or pins hold the both side edges of the membrane similar to the above embodiment so as to stretch the membrane in the width direction by increasing the distance between the opposite membrane-holders with respect to the transportation passage. It is preferable to divide inside the tenter device into different temperature zones and adjust the drying condition for each of the zones.
  • a temperature controller such as an infrared heater and the like. Such dryer may heat the whole area in the tenter device , or may heat according o9
  • the membrane is dried while adjusting the heating temperature of the heater.
  • a method of blowing the dry air, blowing angles of the dry air, flow velocity distribution, flow velocity, temperature difference, flow volume difference, flow volume ratio of each of the air outlets, the use of high specific heat and so forth are properly controlled so as to securely prevent the quality degradation such as the planarity of the membrane during the stretching of the membrane.
  • the clips are used for stretching and holding the both side edges of the film.
  • the clips 64a it is possible to use pins, which hold the membrane 62 by putting the pins through the membrane 62.
  • the portion of the clip directly contacting with the film is made of metal materials or rubber. Rubber is preferable which does not damage the surface of the membrane 62.
  • the clips made of stainless steel are preferable in terms of resistance to the basic solutions.
  • the membrane 62 is preferably stretched in at least one of the casting direction and the width direction by 100.5%-300% with respect to the size of the membrane 62 before the stretching.
  • the membrane 62 is dried by the tenter device 64 until the remaining solvent reaches a predetermined value. Both side edges of the membrane 62 are cut off by the edge slitting device 67. The cut edges are sent to the crusher 103 by a cutter blower not shown. The membrane side edges are shredded into chips by the ⁇
  • the slitting process for the membrane side edges may be omitted. However, it is preferable to perform the slitting process between the casting process and the membrane winding process.
  • the membrane 62 whose side edges are cut off and removed is sequentially transported to the first liquid bath 65 and the second liquid bath 66 through the guide rollers 65b, 65c, 66b and 66c.
  • the membrane 62 is immersed in the first liquid 65a and second liquid 66a in this order.
  • the first liquid 65a for the solvent in the membrane 62
  • the solvent contained in the membrane 62 is reduced.
  • the drying of the membrane 62 in the next process in the drying chamber 69 is promoted.
  • the drying of the membrane is further promoted by substituting the second liquid 66a for the solvent in the membrane 62 by immersing the membrane into the second liquid bath 66.
  • the membrane 62 is transported to the drying chamber 69. Dry air is supplied to the drying chamber 69 to dry the membrane 62 while the membrane 62 is being transported through the drying chamber 69 by the rollers 68.
  • the solvent in the membrane 62 is evaporated together with, for instance, water in the case the membrane 62 is immersed in water.
  • the organic solvent remained in the membrane 62 is efficiently removed.
  • a temperature inside the drying chamber 69 is not particularly limited. However, it is preferable to determine the temperature according to the heat resistance (glass transition point Tg, heat deflection temperature under load, melting point Tm, continuous working temperature and the like) of the solid electrolyte, and the temperature is preferably not more than the Tg.
  • the temperature inside the drying chamber 69 is not less than 120° C and not more than 185° C .
  • the membrane 62 is preferably dried until the remaining solvent reaches less than 5 wt . % . It is preferable to dry the membrane 62 such that the remaining solvent of the membrane 62 is less than 5 wt.%.
  • the solvent vapor generated by drying the membrane 62 in the drying chamber 69 is adsorbed and recovered by the absorbing device 106.
  • the air from which the solvent is removed is supplied to the drying chamber 69 as the dry air.
  • the drying chamber 69 is preferably divided into plural sections so as to change the temperature of the dry air in each section. It is also preferable to provide a predrying chamber (not shown) between the edge slitting device 67 and the drying chamber 69 to predry the membrane 62. Thereby, in the drying chamber 69, an abrupt increase of the membrane temperature is prevented so that changes in shapes and conditions of the membrane 62 are prevented. Instead or in addition to the drying using the dry air as above, drying by decompression, far-infrared rays, microwaves or the like is also used.
  • the membrane 62 After the drying in the drying chamber 69, the membrane 62 is cooled to room temperature in a cooling chamber 71.
  • the humidification chamber is provided between the drying chamber 69 and the cooling chamber 71, it is preferable to spray air whose humidity and temperature are adjusted to desired values to the membrane 62.
  • the temperature inside is not less than 2O 0 C and not ⁇
  • the humidity therein is not less than 40 RH% and not more than 70 RH% . Thereby, curling and winding defects in the membrane 62 are prevented.
  • various processes such as the drying process and the edge slitting and removing process are performed between the membrane peeling process and the membrane winding process.
  • the membrane 62 is mostly supported or transported by using the rollers.
  • driving rollers and non-driving rollers are used for determining the transportation passage of the membrane 62 and improving the transportation stability during the transportation of the membrane 62.
  • the charged voltage during the transportation of the membrane 62 is controlled by using the neutralization device 72 at a desired value.
  • the charged voltage after the neutralization is preferably in a range of -3kV to +3kV.
  • knurling is preferably provided to the membrane by using the knurling roller pair 73. Note that the height of each of projections and depressions is preferably in a range of l ⁇ m to 200 ⁇ m.
  • the membrane 62 is wound by the winding roll 107 of the winding device 76. It is preferable to apply the tension of the desired value to the membrane 62 by using the press roller 108 during the winding of the membrane 62. It is preferable to gradually change the tension applied to the membrane 62 from the start to the end of the winding. Thereby, excessive tightening during the winding is prevented.
  • a width of the membrane 62 is preferably 100mm or more.
  • the present invention is also applicable to the production of thin membranes with the thickness in a range of 5 ⁇ m to 300 ⁇ m.
  • the membrane producing apparatus 233 uses a plastic membrane (hereinafter referred to as a web) 111 wrapped around a casting drum 110 as the support instead of the belt 82 used in the membrane producing apparatus 33.
  • the web 111 is loaded 5 in a web feeding device 112 in a roll form. From the web feeding device 112, the web 111 is fed into the casting drum 110. Above the casting drum 110, the casting die 81 is set close to the web 111.
  • the dope is cast from the casting die 81 onto the web 111 to form the casting membrane 24 on the web 111 while the web 111 0 is being transported. Note that the dope 24 and the casting die 81 are the same as those used in the first embodiment so that the description thereof is omitted.
  • a casting membrane drying device 113 is provided.
  • the casting membrane drying device 113 ,5 is constituted of a drying section 114.
  • the drying section 114 is constituted of a duct 116 having an outlet 116a and a vent 116b, an air blower, a heating device, an opening to introduce outside air and so forth. Dry air 117 is blown from the outlet 116a to the casting membrane 24a in the direction of and parallel 0 to the transporting direction of the web 111. Thus, the evaporation of the solvent is promoted.
  • an air shield plate 118 is necessary between the casting die 81 and the outlet 116a.
  • the casting die 81, the casting drum 110, the outlet 116a and the vent 116b of the casting membrane drying device 113 are provided in a 0 casting chamber 119.
  • the gases other than the solvent vapor in the casting chamber 119 should be recovered and kept at a predetermined amount.
  • the gases other than the solvent vapor in the casting chamber 119 should be recovered and kept at a predetermined amount.
  • the drying method it is also possible to use infrared rays, decompression, far infrared rays and microwaves for drying instead or in addition to the above dry air.
  • the nonwoven plastic film such as polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, nylon 6 film, nylon 6, 6 film, polypropylene film, polycarbonate film, polyimide film or the like is used. It is preferable that the web 111 has chemical stability against the solvent. It is also preferable that the web 111 is heat resistant to withstand the membrane forming temperature. In this embodiment, the PET film is used as the web 111.
  • a feeding speed of the web 111 is preferably in a range of 0.5m/min. to lOOm/min.
  • the surface temperature of the web 111 is properly determined according to the material thereof .
  • the surface temperature is preferably adjusted in a range of -2O 0 C to 100 0 C.
  • the passage for the heat transfer medium (not shown) is formed inside the casting drum 110 to flow the heat transfer medium whose temperature is kept at the predetermined value .
  • the position fluctuations in the vertical direction of the casting drum 110 due to displacements of the rotation center is preferably adjusted to be less than 0.2mm. Defects on the surface of the web 111 should be minimized.
  • the number of pin holes whose diameter is 30 ⁇ m or more is zero, the number of pinholes whose diameter is 10 ⁇ m or more and less than 30 ⁇ m is 1 or less per Im 2 , and the number of pinholes whose diameter is less than 10 ⁇ m is 2 or less per Im 2 .
  • the first and second liquid baths 120, 121 are constituted in the same manner as those in the first embodiment.
  • the first liquid 65a is stored in the first liquid bath 120.
  • the second liquid 66a is stored in the second liquid bath 121.
  • the casting membrane 24a on the web 111 has a self-supporting property.
  • the casting membrane 24a is peeled off from the web 111 by using a peel roller
  • the peeled membrane is referred to as a membrane
  • the membrane 124 is immersed in the second liquid bath 121 by using guide rollers 121b.
  • the solvent contained in the casting membrane 24a is reduced by solvent substitution in the first liquid bath 120 to promote the drying of the membrane 124 in the next drying process in the drying chamber 69.
  • the solvent substitution in the second liquid bath 121 the drying of the membrane 124 is further promoted.
  • the substitution of the first and the second liquids 65a and 66a for the organic solvent contained in the casting membrane 24a and/or the membrane 62 described above is referred to as the solvent substitution.
  • the membrane is transported from the second liquid bath 121 to the drying chamber 69 through the tenter device 64 to further promote the drying. After being dried sufficiently, the membrane 124 is wound by the winding device 76 in the roll form.
  • the installation position of the tenter device 64 is not limited 4b
  • the remaining solvent in the membrane 124 at the time of peeling off from the web 111 is preferably in a range of 200 wt. % to 950 wt. % to the whole solid component.
  • the tenter device 64 of the first embodiment shown in Fig. 2 and/or the drying chamber 69 using the rollers.
  • the casting membrane 24a is dried in the tenter device 64 together with the web 111 in the tenter device 64 and thereafter, the casting membrane 24a is dried in the drying chamber 69 using the rollers.
  • the order is not particularly limited in the present invention.
  • the web 111 is wound by a web winding device 125 in a roll form.
  • both the web feeding device 112 and the web winding device 125 have a turret mechanism.
  • the old web 111 is cut and the new web 111 is adhered thereto.
  • the new web 111 is rotated by a round, the old web 111 is cut off and removed so as to adhere the ends of the new web 111 to form the endless loop.
  • Fig. 5 is a schematic view of a membrane producing apparatus 333 of the third embodiment.
  • the membrane producing apparatus 333 is provided with the web 111 instead of the belt 82 shown in Fig. 2.
  • the casting membrane 24a is peeled off as a membrane 410 after the casting membrane 24a formed on the web 111 is immersed in the first liquid 65a.
  • the same numerals are assigned to the devices and members constituting the membrane producing apparatus 333 which are the same as those in the first and second embodiments shown in Figs. 2 and 4, and descriptions thereof are omitted.
  • the web 111 is loaded in the web feeding device 112 in the roll form in the same manner as that in the second embodiment .
  • the casting chamber 63 is provided with a belt 400 for supporting the web 111.
  • the belt 400 is bridged across drums 401a, 401b to form a passage through which the web 111 passes in the casting chamber 63.
  • the web 111 is fed by the web feeding device 112 to the belt 400 and transported along the passage in the casting chamber 63. Thereafter, the web 111 is transported out of the casting chamber 63.
  • the casting die 81 In the proximity of the passage in the casting chamber 63, the casting die 81 is disposed. The dope 24 is cast from the casting die 81 to the web 111 to form the casting membrane 24a while the web 111 is being transported.
  • the air blowers 91-93 and the air shielding plate 94 are provided in the same manner as those in the first embodiment.
  • the casting membrane 24a is dried by the dry air from the air blowers 91 to 93 while the web 111 is being transported along the passage.
  • the casting membrane 24a is dried until the remaining solvent reaches a predetermined value. Thereafter, the casting membrane 24a together with the web 111 is transported outside the casting chamber 63.
  • the web winding device 125 In the downstream from the casting chamber 63, the web winding device 125 is disposed. The web 111 is transported by the guide rollers and wound by the membrane winding device 125.
  • Guide rollers 405b are provided between the casting chamber 63 and the web winding chamber 125.
  • a first liquid bath 405, a first water remover 415 and the peel roller 123 are disposed in this order.
  • the casting membrane 24a transported from the casting chamber 63 by the web winding device 125 and the guide rollers 405a comes in contact with the first liquid 65a while the casting membrane 24a is supported by the web 111. Thereafter, the casting membrane 24a supported by the web 111 is transported from the first liquid bath 405 to the first water remover 415.
  • Water on the casting membrane 24a supported by the web 111 is removed by the water remover 415.
  • the water remover 415 for instance, blades, an air knife, rolls or the like are used.
  • the air knife is most preferable for the water remover 415 since the air knife removes water most efficiently.
  • the air knife removes the remaining moisture content on the surface of the casting membrane 24a almost completely.
  • the airflow volume is preferably in a range of 10m/s to 500m/s, more preferably, 20m/s to 300ra/s, and most preferably, 30m/s to 200m/s. Note that the above air flow volume is not particularly limited. The air flow volume is properly determined according to the moisture content on the surface of the casting membrane 24a before using the water remover 415 , the transporting speed or the like.
  • a variation range in the airflow velocity distribution in the width direction of the casting membrane 24a is preferably set at 10% or less, and more preferably 5% or less by adjusting the outlet of the air knife or the air supplying method of the air knife. The closer the clearance between the surface of the casting membrane 24a and the outlet of the air knife, the more moisture content on the surface of the casting membrane 24a is removed. However, at the same time, the possibility to damage the surface of the casting membrane 24a by the outlet of the air knife also increases.
  • the air knife is installed such that the clearance between the surface of the casting membrane 24a and the outlet of the air knife is in a range of 10 ⁇ m to 10cm, more preferably 100 ⁇ m to 5cm, and most preferably 500 ⁇ m to lcm. It is preferable to install the air knife and a backup roll on opposite sides of the transportation passage of the casting membrane 24.
  • the backup roll supports the casting membrane 24a so as to stabilize the clearance setting and reduce the flutters, wrinkles and deformations of the casting membrane 24a.
  • the casting membrane 24a which passed through the first water remover 415 is transported to the peel roller 123.
  • the peel roller 123 peels off the casting membrane 24a from the web 111 as the membrane 410 and transport the membrane 410 to the tenter device 64.
  • the tenter device 64 the membrane 410 is dried until the remaining solvent reaches the predetermined value. 5U
  • the tenter device 64 has the same configuration as that shown in Fig. 3 and the description thereof is omitted.
  • a second liquid bath 420 in which the second liquid 66a is stored guide rollers 420b are provided.
  • the membrane 410 whose edges have been cut off and removed by the edge slitting device 67 is transported to the second liquid bath 420 by the guide rollers 420, immersed into the second liquid 66a and transported out of the second liquid bath 420.
  • the solvent substitution is performed by contacting the membrane 410 to the second liquid 66a.
  • the membrane 410 is transported to a second water remover 425.
  • the second water remover 425 has the same structure as that of the first water remover 415 and is used for removing the water from the surface of the membrane 410.
  • the membrane 410 which passed the first water remover 415 is transported to the drying chamber 69.
  • the dry air is blown onto the membrane 410 to dry the membrane 410 while the membrane 410 is being transported.
  • the time for drying the membrane 410 in the tenter device 64 and the drying chamber 69 that is, the time for removing the organic solvent contained in the membrane 410 is shortened by the solvent substitution through the first and second liquids 65a, 66a.
  • the time for drying the membrane 410 is further shortened by removing the water from the surface of the membrane 410 with the use of the first and second water removers 415 and 425.
  • the casting membrane or the membrane is dried before the solvent substitution by the contact of the poor solvent of the solid electrolyte to reduce the remaining solvent in the casting membrane to the predetermined value. Thereby, during the solvent substitution, formation of pores in the casting membrane or in the membrane is prevented. Thus, it becomes possible to obtain the solid electrolyte membrane with very little defects.
  • X is a polymer which is a cation species other than the hydrogen atom, that is, the precursor of the solid electrolyte
  • acid processing proton substitution is performed by contacting the precursor membrane to the solution containing acid which is a proton-donating substituent.
  • the solid electrolyte is generated from the precursor in the precursor membrane.
  • the solid electrolyte membrane is produced from the precursor membrane by the proton substitution.
  • the proton substitution in the present invention is to substitute the hydrogen atom for the cation species other than the hydrogen.atom(s) H in the polymer.
  • the remaining solvent in the precursor membrane is preferably not less than 1 wt . % and not more than 100 wt . % (dry measure). If the drying is continued until the remaining solvent achieves less than 1 wt . % , the drying time becomes too long which is not preferable. If the acid processing is performed to the precursor membrane containing the remaining solvent exceeding 100 wt . % (dry measure) , a percentage of voids becomes too large which is not preferable.
  • the method is not particularly limited to the above as long as the method is capable of removing the acid by contacting the membrane to the water.
  • Water can be sprayed by a method using an extrusion coater or various coating heads such as a fountain coater or a frog mouth coater, or a method using a spray nozzle which is commonly used for humidification of air, painting, automatic washing of a tank and so forth.
  • spraying methods are disclosed in "All about coating", edited by Masayoshi Araki, published by Kako Gijutsu Kenkyukai (Converting Technical Institute), 1999, and are also applicable to the present invention.
  • conical or sector spray nozzles manufactured by Ikeuchi Co . , Ltd. or Spraying Systems Co. , Ltd. can be arranged along a thickness direction of the membrane so as to hit water stream to the entire width.
  • the washing effect becomes higher.
  • the amount of water to be used in washing should be larger than the calculated amount based on a theoretical dilution ratio defined by an equation, (amount of washing liquid [ml/m 2 ]) ⁇ (amount of aqueous acid solution [ml/m 2 ]).
  • the theoretical dilution ratio is defined on the assumption that the whole amount Oo
  • water for washing contributes to dilution of the contact solution containing the acid. Actually, since the whole amount of water does not contribute to form a mixture, a larger amount of water than that derived from the theoretical dilution ratio is used in practice.
  • the amount of water varies depending upon the acid concentration of the solution used, additives, and type of a solvent; however, water is used in an amount providing a dilution ratio of at least 100 to 1000 times, preferably 500 to 10,000 times, more preferably 1,000 to 100,000 times.
  • a predetermined amount of water it is preferable to divide the predetermined amount of water into several portions and wash a polymer membrane several times rather than to use the whole amount of water at a time . The washing effect increases as the number of washings increases.
  • the film is preferably washed for two to ten times.
  • appropriate time intervals and distances are preferably provided between the above washing devices so as to diffuse the ? water on the membrane to dilute the solution containing the acid.
  • the most preferable method is to remove the water from the surface of the solid electrolyte membrane by providing the water remover between the washing devices.
  • the aforementioned first and second water removers 415, 425 are used.
  • the above acid processing and washing are performed between a process for forming the casting membrane and a process for obtaining the membrane product.
  • a first tank and a second tank are provided between the downstream from the casting chamber and the tenter device.
  • the solution containing the acid is stored in the first tank.
  • Water is stored in the second tank.
  • the casting membrane which has been dried is transported to the first tank for the acid processing and then to the second tank for washing.
  • the casting membrane is transported to each tank while being supported by the support, or after the casting membrane is peeled off from the support.
  • the water remover is not particularly limited, and it is possible to use the aforementioned water removers .
  • two liquid baths are provided.
  • at least one liquid bath may be used.
  • two liquid baths are installed in tandem.
  • To contact the membrane with the solution other than immersing the membrane in the liquid baths, spraying, coating and other methods may be used.
  • a solvent having one component or a solvent mixture having two or more components is used for preparing an optimum solution for contacting the membrane depending on the organic solvent used for the membrane production. The organic solvent is more securely removed from the membrane by performing the solution contact process for several times.
  • a membrane width at an arbitrary point in the drying process is Al (mm)
  • a membrane width at a point where the remaining solvent is reduced by 10% from that in the above arbitrary point is Bl (mm)
  • the membrane is dried under the condition Sa ⁇ 5.
  • the driving roller is used for transporting the membrane immediately after being peeled off.
  • elastic modulus of the membrane in the width direction is preferably from 1.5 kg/mm 2 to 400 kg/mm 2 .
  • the roller used in the drying and transporting process has a structure capable of applying the tension outward in the width direction of the membrane.
  • a width of the membrane in the position where the remaining solvent ratio is Yo is C
  • a width at the end of the drying and transporting process is D
  • a diameter of the roller is in a range of 5 cm and 30 cm, especially preferable in a range of 10 cm and 20cm.
  • the maximum coefficient of the friction is preferably in a range of 0.12 and 0.8, the minimum coefficient thereof is preferably in a range of 0.1 and 0.5.
  • a neutralization device 72 to control the charged voltage of the membrane 62 from -5kV to +5kV.
  • the neutralization device 72 is preferably disposed in the proximity of a peeling section (in this embodiment an area close to the peel roller 109) in which the membrane is peeled off from the casting support or at any position between the peeling of the membrane and the completion of the drying in the drying device. More preferably, the charged voltage of the membrane 62 after the neutralization ranges from -3kV to +3kV. It is preferable to use the neutralization device 72 which sprays gas containing ions.
  • the oxygen concentration in the gas containing the ions is preferably 10 vol% or less.
  • Earth leakage resistance of the casting support and/or that of the roller contacting the membrane is preferably 10 6 ⁇ or less.
  • the surface temperature of the membrane is set so as to make the pressure of the solvent vapor 6,650 Pa or less. Further it is preferable to install the neutralization bar or neutralization fiber immediately downstream from the peel roller.
  • the following methods are preferably used to adjust the charged voltage of the membrane in a range of -5kV and +5kV during the membrane formation: for instance, a method in which the material of roller contacting with the membrane is determined according to the electrification table such that the material in a position where the charged voltage is smaller than that of the membrane is selected, a method in which the surface roughness of the casting support (in this embodiment, the belt 82) or the roller surface is made properly rough to reduce the contact area thereof with the membrane, a method in which the matting agent is added in the membrane or applying the substance containing thematting agent onto the membrane surface to reduce the contact area of the membrane with the support or the roller, a method in which membrane conductivity of the membrane is increased by adding the conductive material to the membrane or applying that onto the membrane, a method in which earth leakage resistance is reduced by increasing the relative humidity of the ambience, a method in which a gas is ionized and the ions are sprayed onto the membrane to neutralize the electrical charge on the membrane surface, a method in
  • the neutralization device it is possible to use any device capable of removing or reducing the static electricity of the membrane.
  • the neutralization bar, neutralization fiber or neutralization device of an ion supplying type is preferably used.
  • the neutralization device of the ion supplying type is preferable.
  • the neutralization device of the ion supplying type ionizes the gas by corona discharge, flame plasma, ultraviolet rays, heated metals, radio isotope or the like to generate the ions so as to spray the ions onto a target .
  • the neutralization device using the corona discharge is constituted of an electrode unit incorporating a high pressure transformer, a blowing unit, gas supplying section, controller and so forth.
  • the corona discharge is generated by the electrode unit to ionize the gas.
  • the ionized gas is blown onto a target from the blowing section.
  • Air is normally used in the above method.
  • inactive gas nitrogen, carbon dioxide, argon or the like is used. In terms of cost, nitrogen and carbon dioxide are preferable.
  • the neutralization fiber is a flexible string-like fiber , for instance, 12/300 x 3 produced by Naslon Co., Ltd. is preferably used.
  • a distance between the neutralization device and the membrane is preferably in a range of 10 mm and 100mm.
  • the neutralization device is preferably installed in a position where the peeled membrane reaches the length in a range of 10 mm and 100 mm.
  • the neutralization device is preferably disposed in the proximity of the peel roller. However, it is also possible to install the neutralization device between the casting belt and the peel roller. In consideration of preventing the cutting of the membrane and safety hazards, it is preferable to install the neutralization device downstream from the peel roller.
  • the position to install the neutralization device is preferably 10 mm to 1000 mm away from the peel roller, and more preferably, 10mm to 500 mm away from the peel roller. Especially, the proximity of the peel roller is preferable. It is possible to install the neutralization device on either surface of the membrane .
  • the a first membrane surface comes in contact with a first contact roller, and a second membrane surface comes in contact with a second contact roller after the membrane is peeled off from the belt .
  • the surface of the membrane intimately contacted with the belt during the transportation by the belt is referred to as the first membrane surface.
  • the surface of the membrane exposed to the air during the transportation by the belt is referred to as the second membrane surface.
  • the membrane is dried. At this time, it is preferable to satisfy the following conditions: the diameter of the first contact roller reduces as the roller comes oy
  • the diameter of the second contact roller increases as the roller comes closer to the center portion thereof, and the membrane is dried after being peeled off from the casting belt and transported through the first nip roller.
  • two small rollers come in contact with the side edges of the first membrane surface.
  • the angles which the roller shafts form with the membrane are ⁇ and (180° - ⁇ ' ) , while ⁇ and ⁇ ' satisfy ⁇ > 0° and ⁇ ' ⁇ 90° . Then the second membrane surface is contacted with the first contact roller and dried.
  • the membrane is preferably dried after contacting with the first contact roller changing its position depending on the remaining solvent in the membrane immediately after the peeling, or the surface temperature of the peeled membrane.
  • a vertical slit air at not less than 20 m/s is blown onto the first membrane surface from a nozzle disposed above the membrane.
  • the second membrane surface is contacted with the first contact roller and dried.
  • the distribution of the air velocity in the width direction of the air from the vertical slit slightly increases from a center portion toward both side ends.
  • a lap angle by which the membrane contacts with the first contact roller is changed by changing the position of the second contact roller depending on the remaining solvent in the membrane at the time the membrane is peeled off from the belt .
  • the membrane is contacted with the second contact roller and dried.
  • the surface temperature of the first contact roller reduces from the center portion toward both side portions in the lengthwise direction of the roller.
  • the membrane it is preferable to dry the membrane after satisfying the following condition.
  • the surface temperature of the roller contacting the membrane is Tr, and that of the belt is Tb at the time of peeling off the membrane from the belt, (Tr - Tb) ⁇ 50.
  • the surface temperature Tr has a temperature distribution in which the surface temperature Tr decreases from a center portion toward both side edges in the lengthwise direction.
  • the surface roughness Ra of the roller which contacts with the membrane immediately after the peeling is preferably Ra ⁇ 1.0 ⁇ m.
  • the driving roller it is preferable to provide velocity changes in a range of 1.001 and 1.100.
  • a transporting section 101 is provided. More preferably, a transportation device which transports the membrane without contacting at least the second membrane surface is installed, the number of the rollers contacting the second membrane surface is not more than three, and the transportation distance of the above contactless roller occupies in a range of 10% and 60% of that between immediately after the peel roller and the exit of the tenter device.
  • the contactless roller at least one of the following types is preferable: an air floater type which blows the air on both membrane surfaces , a type which has a means to hold the membrane side edges, or a suction roll type which only contacts the first membrane surface .
  • the membrane having the remaining solvent in a range of 20 wt . % and 130 wt . % at the ambient temperature of not more than 4O 0 C is preferably transported through the contactless roller.
  • rollers for transporting the membrane without contacting with the membrane air floater type, a type capable of holding the membrane side edges by the clips or nip rollers or a suction roller type is used.
  • a pair of movable belts of the caterpillar type or plural pairs of nip rollers to hold the both side edges of the membrane without contacting the membrane surfaces.
  • those with projections and depressions are capable of securely holding the membrane side edges. For that reason, the nip rollers with projections and depressions just like those for embossing use and with male/female coupling are preferable.
  • the shapes of the projections and depressions are preferably acute-angled, groove-like shapes or the like to securely hold the membrane.
  • the pressure of the plural pairs of the nip rollers applied to the membrane is preferably in a range of 30 Pa and 500 Pa, and more preferably in a range of 50 Pa and 200 Pa.
  • the membrane containing the remaining solvent in a range of 10 wt.% and 150 wt . % is transported while being contacted with roller(s) whose surface roughness Ry is 0.6 ⁇ m or less, and the surface energy thereof is in a range of 70 mN/m and 100 mN/m at 20 0 C.
  • the first roller of the above roller(s) is the peel roller, and the roller only contacts with the second membrane surface.
  • the surface of the roller is plated with the hardened chrome.
  • the roller diameter is 85 - 300 mm.
  • the solution casting device has a cleaner for cleaning the roller and the surface thereof .
  • the cleaner moves in the roller shaft direction.
  • the solution casting device also has a means to apply the organic solvent onto the roller while the cleaner moves in the roller shaft direction, and a means to wipe the roller surface disposed adjacent to the above means to apply the organic solvent .
  • the organic solvent is supplied by a capillary phenomenon, or the roller is wiped by the non-woven cloth containing the organic solvent.
  • the solvent which is the good solvent of the solid electrolyte in which the solid electrolyte is soluble or a solvent mixture of the good solvent and the poor solvent of the solid electrolyte.
  • a hollow body driving roller capable of decompressing the hollow body to absorb the membrane during transportation. Further, the following conditions are more preferable.
  • Plural absorption openings are formed at least a part of the peripheral walls of the driving roller in a lengthwise direction all through the roller, and the absorption openings are covered with metal nets whose mesh size is in a range of 0.5 mm 2 and 50 mm 2 . It is also possible to use the covers formed of porous, plates . An area of the micropore is in a range of 0.5 mm 2 and 50 mm 2 .
  • a ratio of the portion in which the absorption openings are formed in the driving roller in the width direction with respect to the entire width of the membrane is in a range of 0.1 and 1.
  • the absorption openings are circular, oval or the polygonal which is pentagonal or more.
  • the size of the absorption openings is in a range of 1 mm 2 and 100 mm 2 .
  • At least one absorption opening is formed in an area of 30 mm x 30 mm.
  • the outer diameter of the driving roller is in a range of 65 mm and 450 mm.
  • the lids are provided for closing the absorption opening provided on both side walls of the driving roller.
  • a driving shaft driven by a motor or the like is fixed to one of the opposing lids with respect to the roller. Through the driving shaft, a suction passage is formed which is connected to the inside the driving roller. Inside the driving roller is decompressed by a vacuum pump through a suction passage. The suction air by the vacuum pump is transported to the solvent recovery device.
  • the solvent recovery device the flux in the solvent dissolving the solid electrolyte is recovered.
  • the membrane is passed through a transporting section in which a group of rollers are arranged in staggered arrangements.
  • the surface temperature of the membrane is heated by the above rollers to 50° C - 100° C.
  • the passing time of the membrane through the transporting section is in a range of 10 seconds and 70 seconds. More preferably, the largest distance between the rollers is not more than a membrane width at the peeling of the membrane.
  • the roller distance is not more than 900 mm.
  • the second membrane surface is contacted with the transportation device which is one of the drum and the roller of the arch type.
  • the membrane is transported such that the remaining solvent reaches in a range of 30 wt . % and 120 wt.%.
  • the membrane side edges are heated such that the surface temperature thereof reaches 5O 0 C or above by near-infrared radiation, far-infrared radiation or blowing of the heated air. After the heating, it is also possible to cool the membrane side edges by using the cooling roller. Further, it is preferable to contact the second membrane surface with the organic solvent having dissolving property or swelling property while transporting the membrane having the remaining solvent in a range of 30 wt. % and 120 wt.% between the peel roller and the entrance of the tenter.
  • a tension cut-off device is installed between downstream from the peel roller and before the winding chamber. The membrane is transported with the tension in a range of 1 N/m and 100 N/m between after the peeling and before the tension cut-off device.
  • a distance between the membrane peeling position and the tension cut-off device is equal to the membrane length in a range of 2 m and 90m.
  • the membrane is transported between the membrane peel position and the tension cut-off device through guide rollers or the air floats. A part or all of the rollers are tendency rollers .
  • a stretching and contraction ratio in the transportation direction is MD
  • that in the width direction is TD, -4% ⁇ MD-TD ⁇ 4% and -6% ⁇ MD + TD ⁇ 6%.
  • the stretching and contraction ratio of the membrane in the width direction in a region after peeling the membrane from the belt and before stretching the membrane for the first time in the width direction is TD', TD' ⁇ -6%.
  • the transportation time between the belt and membrane peeling position is not more than 10 seconds
  • the temperature of an area 10 cm outside from the side edges of the membrane on the roller and 2 cm away from the roller surface is in a range of the boiling point and (boiling point + 3O) 0 C.
  • the organic solvent is coated, sprayed, fine sprayed, or the like.
  • the amount of the solvent is increased or decreased depending on the size of the curling.
  • the organic solvent is coated to the extent that the additive should not be eluted.
  • the organic solvent is applied onto the whole area of the second membrane surface by providing a coating roller (or the peel roller) on opposite side of the non-driving roller contacting the first membrane surface and using the non-driving roller as the back roller.
  • the concentration of the organic solvent used for spraying or fine-spraying onto the second membrane surface is in a range in which an explosion does not occur.
  • the organic solvent After contacting the organic solvent with the membrane, the organic solvent is evaporated or discharged to the outside of the system by suction as soon as possible.
  • the organic solvent having the dissolving or swelling properties is used.
  • the mixing ratio (the weight ratio) is preferably in a range of 20/80 and 90/10, and determined depending on the effect of the combination of the organic solvents. In this case, it is preferable to heat the membrane from the second membrane surface side.
  • any devices capable of heating the both membrane side edges are used.
  • the curling is corrected by, for instance, heating the membrane side edges on the roller, interposing the membrane between a pair of heating roller, or indirectly heating the membrane by using the near-infrared irradiation or far-infrared irradiation. It is preferable to supply the heated air through a nozzle, a pipe, or a pipe having punch holes . It is preferable to use the roller having a narrow width such as the nip rollers for the heating rollers to contact the membrane side edges.
  • the heated portions of the heating rollers are preferably within 100 mm, and more preferably within 50 mm from the membrane side edges.
  • the heating temperature is preferably in a range of 50" C and 200° C, and more preferably in a range of 80° C and 150° C.
  • the metal rollers are preferably used for the heating rollers .
  • ceramic rollers are more preferable. In this case, the ceramic rollers are indirectly heated by infrared rays .
  • the curling may occur again. For that reason, it is possible to cool the heated portion of the membrane.
  • Methods for cooling are not particularly limited. For instance, the cooled air is blown onto the membrane side edges or the cooled roller is contacted thereto. To be more specific, the cooling temperature is lower than the heating temperature by 10° C or more.
  • the peeling it is also possible to cut off the curled portions within a width of not more than 50 mm from the membrane side edges in a region where the remaining solvent in the membrane is not more than 50 wt . % . Even if the curled portions are cut off , in the case where the large amount of solvent is remaining in the membrane, the curling may likely to occur again. For that reason, it is preferable to cut off the membrane just before the entrance of the tenter device or the driving roller.
  • the rollers may be deformed due to the pressing force of the membrane against the rollers when transporting the membrane after the membrane is peeled off from the belt.
  • the thin membrane containing a relatively large amount of remaining solvent the additives precipitating and evaporating from the membrane adhere to and contaminate the rollers. Such contaminations are transferred to the membrane. Dents may also be formed on the membrane by being pressed by such additives .
  • the tension is small, the rotation of the roller is interfered. As a result, the membrane is damaged by scratches and so forth.
  • the tension should be increased, resulting in contaminations and dents on the membrane.
  • the roller diameter is preferably 85 mm - 300 mm, more preferably 100 mm - 200 mm.
  • the temperature of the membrane is preferably kept higher than the highest melting point of the contained additive.
  • the distances between the clips or pins are increased or reduced in the lengthwise direction by using a simultaneous biaxial stretching device.
  • the membrane is stretched smoothly by driving the clips in the linear-driving method, preventing the ruptures of the membrane.
  • the rollers are rotated with different peripheral speeds to stretch the membrane in the lengthwise direction. It is possible to combine the stretching methods and/or carry out the stretching process in plural steps, for instance, the lengthwise stretching and the widthwise stretching are carried out alternately, or the stretching in the same direction may be repeated. It is also possible to preheat the membrane by the heating device before stretching. Thereby, the changes in shapes and conditions of the membrane caused by the temperature changes are bo
  • the heating temperature of the dry air is preferably in a range of (Tg of the solid electrolyte membrane - 20° C) to (Tg +10° C) .
  • the heating time is preferably in a range of one second to 180 seconds.
  • the membrane is stretched in the room temperature or under heated conditions .
  • the heating temperature is not more than the Tg of the membrane.
  • Uniaxial or biaxial methods are used for stretching the membrane.
  • the membrane is stretched while drying the membrane and it is especially preferable in the case the solvent remains in the membrane.
  • the membrane is stretched if the membrane winding speed is higher than the membrane peeling speed by adjusting the roller speeds.
  • the membrane is also stretched by gradually increasing the tenter width. It is also possible to stretch the membrane by using the stretching device such as the tenter device after drying. It is more preferable to use a long stretching device.
  • the stretching ratio of the membrane that is, a ratio of the stretched length with respect to the length before the stretching is preferably 0.5% - 300%, more preferably 1% - 200%. The stretching in a range of 1% and 100% is especially preferable.
  • Stretching speed is preferably in a range of 5%/min and 1000%/min, more preferably 10%/min and 500%/min.
  • the heating during the stretching is preferably carried out by using the heat rollers and/or radiation heat source (IR heater and the like) and heated air.
  • IR heater and the like radiation heat source
  • heated air To increase the uniformity of the temperature, a constant temperature bath may be used.
  • a ratio of a distance (L) between the rollers and a membrane width (W) of the phase difference plate (L/W) is preferably in a range of 2.0 and 5.0.
  • a difference in the tension applied to the membrane in the transportation direction before and after the tenter device is preferably 8 N/mm 2 or less to obtain ' the thin-membrane.
  • the membrane is dried by providing the transporting section and the tenter device. If the membrane is predried in the transporting section, the temperature of the membrane does not increase abruptly. Thereby, the changes in the shape of the membrane and degradation of the material, that is, the polymer are prevented.
  • the heating temperature Tl of the drying device is not less than (Tg-60.) 0 C, and the temperature T2 in the relaxation process is not more than (Tl-10) 0 C.
  • the stretching ratio of the membrane with respect to the membrane just before the stretching and drying process is in a range of 0% and 30%.
  • the relaxation ratio of the membrane in the relaxation process is in a range of -10% and 10%.
  • the heating portion into the clips . It is more preferable to provide a device for removing impurities between the membrane and the clips in the tenter by spraying a gas or liquid, using a brush and the like.
  • the remaining solvent in the membrane at the time of contacting with the clips or pins is not less than 12 wt . % and not more than 50 wt . % .
  • the surface temperature of the portion of the membrane contacting with the clips or pins is not less than 60° C and not more than 200° C, more preferably not less than 80°C and not more than 120 0 C.
  • the following conditions are preferably satisfied.
  • Lt (m) when the length of the portion of the membrane held by the clips in the above tenter device is Ltt, and when the ratio of Ltt/Lt is Lr, Lr is 1.0 ⁇ Lr ⁇ 1.99. More preferably, the membrane is held by the clips without the clearance between the adjacent clips.
  • the number of the pins per a unit area in an inner side of a film holding member with respect to the membrane is larger than that in an outer side to prevent ruptures, wrinkles and slacks on the membrane, and transportation failures.
  • the pins holding the membrane side edges should be cooled such that the temperature of the pins are less than the membrane foaming temperature.
  • the film holding member including the pins in the tenter device is cooled to make the temperature of the portion of the membrane surface contacting the film holding member not exceeding the temperature at which the membrane becomes the gel-like state.
  • the multi-zone tenter has a configuration in which two or more tenter devices are provided, or a membrane is stretched in at least two steps by using the ⁇
  • the membrane is heated by providing a temperature gradient to prevent unevenness in the membrane.
  • the membrane is stretched when the remaining solvent is in a range of 2 wt . % and 10 wt.% to total components in the membrane.
  • a dope A and a dope B are prepared and both dopes A and B are co-cast on the support such that the dope A forms a core layer and the dope B forms a surface layer.
  • the dope A contains resin(s), additive(s) and organic solvent (s) .
  • the dope B contains resin(s) and organic solvent (s) .
  • the dope B may not contain additives at all or contain a lower additive amount than the dope A.
  • the dope is co-cast to form the casting membrane on the support, and the organic solvent in the casting membrane is evaporated until the casting membrane becomes peelable from the support. Thereafter, the casting membrane is peeled off from the support as the membrane, and the membrane is stretched at least in a uniaxial direction by 1.1 times to 1.3 times when the membrane contains the remaining solvent in a range of 3 wt . % and 50 wt.%, more preferably by 1.1 times to 3.0 times at the drying temperature in a range of 140° C and 200 0 C.
  • the amount of the additives contained in the dope A is in a range of 1 wt . % and 30 wt.% with respect to the resin.
  • the amount of the additive contained in the dope B is in a range of 0 wt.% and 5 wt.% with respect to the resin. It is preferable that the additive is the anti-oxidizers or the plasticizers .
  • the preferable drying conditions depending on the remaining solvent are as follows .
  • the air blowing angle from the air outlet is in a range of 30° and 150° with respect to the membrane and distribution of air flow velocity on the membrane in the direction extended from the air outlet is determined with reference to an upper limit of the air flow velocity, until the remaining solvent reaches 4 wt.%, the dry air whose difference between the upper and lower limits of the air flow velocity is not more than 20% of the upper limit is blown onto the membrane for drying.
  • the air flow velocity of the dry air over the membrane surface is preferably in a range of 0.5 m/s and 20m/s. In the case the remaining solvent is not less than 4 wt .
  • the air flow velocity of the dry air over the membrane surface is preferably in a range of 0.5 m/s and 40m/s, and the difference between the upper and lower limits is 10% or less of the upper limit.
  • the remaining solvent is not less than 4 wt . % and less than 200 wt . % , (the air flow volume of the dry gas supplied from below the membrane) / (that from above the membrane) is 0.2 ⁇ q ⁇ 1.
  • At least one kind of gas is used for the drying gas and the average specific heat is in a range of 31.0 J/K'mol and 250J/K*mol.
  • the concentration of the organic solvent which is liquid in the room temperature contained in the dry gas is 50% or less.
  • the slack preventing device prevents the, slacks in the width direction. More preferably, the slack preventing device is a roller which is rotated at an angle in range of 2° and 60° in the width direction, and has a suction device above the membrane and an air blower which blows the air from beneath the membrane. It is also possible to introduce the membrane peeled off from the support into the tenter device at a certain angle with respect to the membrane.
  • the membrane transporting apparatus transporting the membrane while applying tension to the membrane in the width direction is used after the membrane is peeled off from the support at the time when the remaining solvent is in a range of 50 wt . % and 12 wt . % is used.
  • the membrane transporting apparatus has a membrane detecting device, a membrane holding device and at least two variable bending points .
  • the membrane width is calculated from the detection signal from the membrane detecting device so as to change the positions of the bending points .
  • a guide plate for preventing the curling of the membrane side edges at least on the lower side of the upper and lower sides of both the side edges of the membrane in the tenter device proximity to the entrance thereof .
  • the surface of the guide plate contacting with the membrane is constituted of a resin section and a metal section. More preferably, the resin section is disposed in the upstream of the guide plate and the metal section is disposed in the downstream of the guide plate with respect to the transportation direction of the membrane.
  • a height difference (including a slope) between the resin section and the metal section is not less than 500 ⁇ m.
  • the distance between the resin and metal sections with respect to the membrane in the widthwise direction is in a range of 2 mm and 150mm, more preferably in a range of 5 mm and 120 mm.
  • the resin section of the guide plate contacting with the membrane is formed by applying surface resin processing or resin coating onto a metal guide base plate.
  • the resin section of the guide plate is formed of resin.
  • the distance between the upper and lower guide plates are in a range of 3 mm and 30 mm.
  • the distance between the upper and lower guide plates are increased in the widthwise direction of the membrane by 2 mm or more per the width of 100 mm.
  • a length of the upper and lower guide plates is in a range of 10 mm and 300 mm, and the guide plates are arranged in a staggered arrangement .
  • the upper and lower guide plates are staggered by in a range of -200mm and +200 mm.
  • the surface of the upper guide plate contacting with the membrane is formed only of the resin or the metal.
  • the resin section of the guide plate is formed of Teflon (registered trademark) .
  • the metal section is formed of stainless steel.
  • the surface roughness of the membrane contacting surface of the guide plate, that is, the resin section and/or the metal section is not more than 3 ⁇ m.
  • the upper and lower guide plates for preventing the curling in membrane ' side edges are preferably- disposed between the end position where the membrane is peeled off from the support and the entrance of the tenter device, especially in the position close to the entrance of the tenter device .
  • the membrane is stretched and dried in the stretching device at the time the remaining solvent in the membrane reaches in a range of . 50 wt . % and 12 wt . % . Further, at the time the remaining solvent reaches 10 wt . % or less, the pressure in a range of 0.2kPa and 1OkPa is applied onto both membrane surfaces by a pressurizing device. More preferably, application of the tension is stopped at the time the remaining solvent reaches 4 wt . % or more.
  • the nip rollers are used for applying the pressure to the membrane surfaces, one to eight pairs of the nip rollers are preferably used.
  • the temperature is preferably in a range of 100° C and 200 0 C.
  • the producing method in which a solid electrolyte solution is cast onto the support and the membrane is continuously peeled off and dried satisfies the following conditions: 0 ⁇ ratio of contraction by drying (%) ⁇ 0.1 x amount of remaining solvent in the membrane at the peeling (wt .%) , More preferably, in the case the amount of the remaining solvent is in a range of 40 wt . % and 100 wt . % after the peeling, the remaining solvent is reduced by at least 30 wt . % or more while the. membrane side edges are held by the tenter transportation.
  • the remaining solvent of the peeled membrane at the entrance of the tenter device is in a range of 40 wt . % and 100 wt . % .
  • the remaining solvent at the exit of the tenter device is in a range of 4 wt.% and 20 wt . % .
  • the tension applied to the membrane in the transportation direction of the membrane inside the tenter device is increased from the entrance to the exit of the tenter device.
  • the tension of the membrane in the transportation direction and that in the widthwise direction are approximately equal .
  • the method for stretching the membrane produced by casting there are method for stretching while heating, and that using the solvent.
  • the membrane is preferably stretched at the temperature under Tg.
  • the dried membrane is contacted with the solvent and then stretched.
  • two or more sorts of dopes are co-cast to produce a solid electrolyte membrane.
  • the co-casting method there are a simultaneous co-casting method in which two or more sorts of the dopes are simultaneously cast, or a sequentially casting method in which two or more sorts of the dopes are sequentially cast .
  • the casting die with a feed block or a multi-manifold type casting die can be used.
  • one of two surface layers preferably occupies in a range of 0.5% and 30% of the whole membrane thickness.
  • the concentration of the dopes are previously adjusted such that the higher viscosity dope covers over the low viscosity dope at the time of casting.
  • the dope on the surface sides has a larger ratio of the poor solvent compared to the inner dope.
  • the solid electrolyte membrane by putting the solid electrolyte in the micropores of a so-called porous substrate in which a plurality of micropores are formed.
  • a method in which the solid electrolyte is put in the micropores by applying a sol-gel solution containing the solid electrolyte onto the porous substrate a method in which the solid electrolyte is filled in the micropores by immersing the porous substrate in the sol-gel solution and the like.
  • the porous substrate porous polypropylene, porous polytetrafluoroethylene, porous cross-linked heat-resistant polyethylene, porous polyimide and the like are preferably used.
  • the membrane by processing the solid electrolyte into a fiber-form and fill the voids in the fibers with other polymers , and forming the fibers into the membrane.
  • the polymer for filling the voids it is possible to use the additives described in this specification .
  • the solid electrolyte membrane of the present invention is suitably used for the fuel cell, in particular, for the proton conductive membrane in a direct methanol full cell.
  • the solid electrolyte membrane is used as a component of the fuel cell interposed between the two electrodes of the fuel cell.
  • the solid electrolyte membrane of the present invention is used for the electrolyte in various batteries such as a redox flow battery and the lithium battery, a display element, an electrochemical sensor, a signal transmission medium, a capacitor, electrodialysis, electrolyte membrane for electrolysis, a gel actuator, salt electrolyte membrane and proton exchange membrane.
  • batteries such as a redox flow battery and the lithium battery, a display element, an electrochemical sensor, a signal transmission medium, a capacitor, electrodialysis, electrolyte membrane for electrolysis, a gel actuator, salt electrolyte membrane and proton exchange membrane.
  • Fig. 6 is a section view illustrating a configuration, of the MEA.
  • An MEA 131 is constituted of the membrane 62, and an anode 132 and cathode 133 placed opposite to each other.
  • the membrane 62 is interposed between the anode 132 and the cathode 133.
  • the anode 132 is constituted of a porous conductive sheet 132a and a catalyst layer 132b contacting the membrane 62.
  • the cathode 133 is constituted of a porous conductive sheet 133a and a catalyst layer 133b contacting the membrane 62.
  • the porous conductive sheets 132a, 133a, carbon paper and the like are used.
  • the catalyst layers 132b, 133B are formed of a dispersion in which carbon particles are dispersed into the proton conductive material.
  • the carbon particles support a catalyst metal thereon such as platinum particles.
  • As the carbon particles there are ketjen black, acetylene black, carbon nanotubes .
  • As the proton conductive material for instance, Nafion (registered trademark) and the like are used. The following methods are preferably applied for producing the MEA 131:
  • Proton conductive material coating method a catalyst paste (ink) including a carbon supporting active metal, a proton conductive material and a solvent is directly applied on both surfaces of the membrane 62, and a porous conductive sheets 132a, 133a are thermally adhered under pressure thereto to construct a 5-layered MEA.
  • Porous conductive sheet coating method A liquid containing the material for the catalyst layer 132b, 133b, for instance, the catalyst paste is applied onto the porous conductive sheet to form a catalyst layer thereon, and a solid electrolytic membrane is adhered thereto under pressure to construct a 5-layered MEA.
  • a coating liquid containing materials of the catalyst layers 132b, 133b is previously prepared.
  • the coating liquid is applied onto the support (or the web) and dried.
  • the supports (or the webs) on which the catalyst layers 132b, 133b are formed are thermally adhered to both surfaces of the membrane 62 such that the catalyst layers 132b, 133b contact the membrane 62.
  • the membrane 62 interposed by the catalyst layers 132b, 133b is sandwiched between the porous conductive sheets 132a, 133a.
  • the catalyst layers 132b, 133b are airtightly adhereing the membrane to produce the MEA 131.
  • Fig. 7 is a section view illustrating a configuration of the fuel cell.
  • the fuel cell 141 is constituted of the MEA 131, a pair of separators 142 , 143 for sandwiching the MEA 131 , current collectors 142 which are formed of stainless nets attached to the separators 142, 143, and gaskets 147.
  • the anode-side separator 142 has an anode-side opening 143 formed therethrough; and the cathode-side separator 142 has a cathode-side opening 16 formed therethrough.
  • Vapor fuel such as hydrogen or alcohol (e.g. , methanol) or liquid fuel such as aqueous alcohol solution is fed to the cell via the anode-side opening 15; and an oxidizing gas such as oxygen gas or air is fed thereto via the cathode-side opening 152.
  • a catalyst that supports active metal particles of platinum or the like on a carbon material may be used.
  • the particle size of the active metal particles generally used is in a range of 2 nm to 10 nm. Active metal particles having a smaller particle size may have a large surface area per the unit mass thereof, and are therefore advantageous since their activity is higher. If too small, however, the particles are difficult to disperse with no aggregation, and it is said that the lowermost limit of the particle size is 2 nm or so.
  • cathode In hydrogen-oxygen fuel cells, the active polarization of cathode (air electrode) is higher than that of anode (hydrogen electrode). This is because the cathode reaction (oxygen reduction) is slow as compared with the anode reaction.
  • anode hydrogen electrode
  • platinum-based binary alloys such as Pt-Cr, Pt-Ni, Pt-Co, Pt-Cu, Pt-Fe.
  • platinum-based binary alloys such as Pt-Ru, Pt-Fe, Pt-Ni, Pt-Co, Pt-Mo, and platinum-based ternary alloys such as Pt-Ru-Mo, Pt-Ru-W, Pt-Ru-Co, Pt-Ru-Fe, Pt-Ru-Ni, Pt-Ru-Cu, Pt--Ru--Sn, Pt-Ru-Au.
  • platinum-based binary alloys such as Pt-Ru, Pt-Fe, Pt-Ni, Pt-Co, Pt-Mo
  • platinum-based ternary alloys such as Pt-Ru-Mo, Pt-Ru-W, Pt-Ru-Co, Pt-Ru-Fe, Pt-Ru-Ni, Pt-Ru-Cu, Pt--Ru--Sn, Pt-Ru-Au.
  • carbon material for supporting the active metal acetylene black, Vulcan XC-72, ketjen black, carbon
  • the catalyst layer 132b, 133b have following functions: (1) transporting fuel to active metal, (2) providing the reaction site for oxidation of fuel (anode) or for reduction thereof (cathode) , (3) transmitting the electrons released by the redox reaction to the current collector 146, and (4) transporting the protons generated in the reaction to solid electrolytic membrane.
  • the catalyst layers 132b, 133b must be porous so that liquid and vapor fuel may penetrate the pores .
  • the active metal catalyst supported by the carbon material works for (2) ; and the carbon material also works for. (3) .
  • a proton conductive material is mixed into the catalyst layers 132b, 133b.
  • the proton conductive material mixed in the catalyst layers 132, 133b is not particularly limited provided that it is a solid that has a proton-donating group.
  • Polymer compounds having acid-residue used for the membrane 62 for instance, perfluorosulfonic acids such as typically Nafion; phosphoric acid-branched poly(meth)acrylates; sulfonated, heat-resistant aromatic polymers such as sulfonated polyether-ether ketones, sulfonated polybenzimidazoles are preferably used.
  • the material of the membrane 62 that is, the solid electrolyte is used for the material of the catalyst layers 132b, 133b, the catalyst layers 132b, 133b and the membrane 62 are made of the material of the same type. For that reason, the electrochemical contact between the solid electrolytic membrane and the catalyst layer becomes high, which is more advantageous in view of the proton conduction.
  • the amount of the active metal supporting the active metal is preferably from 0.03 to 10 mg/cm 2 in view of cell output and the cost efficiency.
  • the amount of the carbon material that supports the active metal is preferably from 1 to 10 times the mass of the active metal.
  • the amount of the solid electrolyte is preferably from 0.1 to 0.7 times the mass of the active metal-supporting carbon .
  • the anode 132 and the cathode 133 serve to prevent interference in current collection and gas permeation due to water accumulation.
  • the carbon papers and carbon fibers are commonly used for the anode 132 and the cathode 133. It is also possible to perform polytetrafluoroethylene (PTEF) processing to the carbon paper and carbon fibers for repelling the water.
  • PTEF polytetrafluoroethylene
  • the MEA is preferably incorporated in the battery.
  • Sheet resistivity measured by an AC impedance method when the fuel is loaded is preferably 3 ⁇ cm 2 or less, more preferably l ⁇ cm 2 and most preferably 0.5 ⁇ cm 2 or less .
  • the sheet resistivity is obtained by a product of an actually measured value and a sample area.
  • Fuel for the fuel cell is described.
  • anode fuel hydrogen, alcohols (e.g., methanol, isopropanol, ethylene glycol), ethers (e.g., dimethyl ether, dimethoxymethane, trimethoxymethane) , formic acid, boron hydride complexes, ascorbic acid and the like are used.
  • oxygen including oxygen in air
  • hydrogen peroxide and the like are used for cathode fuel.
  • oxygen (including oxygen in air), hydrogen peroxide and the like are used.
  • aqueous methanol having a methanol concentration of from 3 to 64 wt.% is used as the anode fuel.
  • 1 mol of methanol requires 1 mol of water, and the methanol concentration in this case corresponds to 64 wt.% .
  • a higher methanol concentration in fuel is more effective for reducing the weight and the volume of the cell including the fuel tank of the same energy capacity.
  • the higher methanol concentration tend to reduce the cell output due to the so-called crossover phenomenon in which methanol penetrates through the solid electrolyte and reacts with oxygen at the cathode to reduce the voltage.
  • the crossover phenomenon is remarkable which reduces the cell output.
  • the optimum concentration of methanol is determined depending on the methanol permeability through the solid electrolytic membrane used.
  • the cathode reaction formula in direct methanol fuel cells is (3/2) O 2 + 6H + + 6e ⁇ ⁇ H 2 O), and oxygen (generally, oxygen in air) is used as the fuel in the cells.
  • the method (2) a method not using such auxiliary device, that is, a passive method, for example, the liquid fuel is supplied through capillarity or by free-fall, and vapor fuel is supplied by exposing the catalyst layer to air. It is also possible to combine these methods.
  • the method (1) has some advantages in that water formed in the cathode area is circulated, and high-concentration methanol is usable as fuel, and that air supply enables high output from the cells, while it is difficult to downsize the cell because a fuel supply unit is necessary.
  • the method (2) enables to downsize the cells, while the fuel supply rate is readily limited and high output from the cells is often difficult .
  • the unit cell voltage of fuel cells is generally at most 1 V. It is desirable to stack up the unit cells in series, depending on the necessary voltage for load.
  • a plane stacking in which unit cells are arranged on a plane, and a bipolar stacking in which unit cells are stacked up via a separator with a fuel passage formed on both sides thereof are used.
  • the cathode air electrode
  • the plane stacking is suitable for small-sized fuel cells.
  • MEMS technology in which a silicon wafer is processed to form a micropattern thereon and fuel cells are stacked on the processed silicon wafer.
  • Fuel cells are used in various appliances, for example, for automobiles , electric and electronic appliances for household use, mobile devices and the like.
  • direct methanol fuel cells enable downsizing, lightweight and do not require charging. Having such advantages, they are expected to be used for various energy sources for mobile appliances and portable appliances.
  • mobile appliances in which fuel cells are favorably used include mobile phones , mobile notebook-size personal computers, electronic still cameras , PDA, video cameras , mobile game drivers , mobile servers , wearable personal computers, mobile displays and so forth.
  • the portable appliances in which fuel cells are favorably used include portable generators, outdoor lighting devices, pocket lamps, electrically-powered (or assisted) bicycles and so forth.
  • fuel cells are also favorable for power sources for robots for industrial and household use and for other toys. Moreover, they are further usable as power sources for charging secondary batteries that are mounted on these appliances. [Example 1]
  • examples of the present invention are described.
  • the example 1 is described in detail .
  • examples 2-8 only the conditions which differ from those of the example 1 are described.
  • the examples 1, 2, 5-8 exemplify the embodiments of the present invention.
  • the most preferable examples are the examples 7 and 8.
  • the examples 3 and 4 are the comparison experiments Of 1 the examples ⁇
  • the material A and the solvent are mixed in the following composition to solve the solvent in the material A to produce the solid electrolyte dope 24 of 20 wt . % .
  • the dope 24 is referred to as the dope A.
  • the material A is a sulfonated polyacrylonitrile butadiene-styrene with the sulfonation degree of 35%.
  • Solvent N, N-dimethylformamide 400 pts.wt.
  • the material A is prepared by the following synthesis .
  • the crystal is washed by an aqueous solution containing water and acetonitrile at a ratio of 1 to 1. Thereafter, the 4- (4- (4-pentylcyclohexyl) phenoxymethyl) styrene is dried by the air .
  • a substance of the following composition is heated up to 6O 0 C.
  • Polymerization is performed by dropping a mixture of the following composition onto the mixture of the above composition for 60 minutes to carry out the polymerization.
  • the dope A is cast from the casting die 81 to the belt 82 to form the casting membrane 24a.
  • the dry air in a temperature range of 80° C and 120° C is blown onto the casting membrane 24a by using the air blowers 91 to 93 until the remaining solvent reaches 30 wt. % with respect to the solid, components.
  • the casting membrane 24a is peeled off as the membrane 62 from the belt 82.
  • the membrane 62 is transported to the tenter device 64, and then through the tenter device 64 while the side edges of the membrane 62 are held by the clips 64a. In the tenter device 64, the membrane 62 is dried by using the air blower 64b.
  • the clips 64a are cooled by supplying the heat transfer medium of 20 0 C.
  • the clips 64a are transported by the chains, and the velocity fluctuations of the sprockets are 0.5% or less.
  • Inside the tenter device 64 is divided in three sections, and the drying temperature of each section is 120, 130, 140 from the upstream side.
  • the gas composition of the dry air is a saturated gas concentration at -1O 0 C.
  • the membrane 62 is stretched in the width direction during the transportation thereof. The width of the membrane 62 is stretched by 150% relative to that before the stretching.
  • a difference in the stretch ratios inside the tenter device 64 between two arbitrary points 10 mm away from the clip start position is 10% or less , and that 20 mm away from the clip position is 5% or less.
  • a ratio of the distance between the clip start position and clip end positions with respect to the distance between the entrance and the exit of the tenter device 62 is 90%.
  • the solvent vapor inside the tenter device 64 is condensed and liquefied at -1O 0 C and recovered.
  • the exit temperature of the condenser is -8 0 C.
  • the moisture of the condensed solvent is adjusted 0.5 wt . % or less and reused for the dope production.
  • the clips 64a release the side edges of the membrane 62. Then, the side edge portions ⁇ 6 313918
  • the edge slitting device 67 As the edge slitting device 67, an NT-type cutter is used to cut the side edges by 40mm from the membrane edge.
  • the cut-off membrane side edges are sent to the crusher 103 by the cutter blower (not shown) shredded into chips having average size of 80 mm 2 .
  • the chip together with the solid electrolyte flake are used for the material for preparing the dope.
  • Air inside the tenter device 64 is substituted by the nitrogen gas to keep the oxygen concentration at 5 vol% in the dry ambience .
  • first and second liquids 65a and 66a which are methanol and water solutions at the ratio of 1 to 1 in the first and second liquid baths 65 and 66 to sufficiently substitute the first and second liquids 65a and 66a for N, N-dimethylformamide.
  • the first and second liquids 65a and 66a are insulated at 6O 0 C.
  • the membrane 62 is transported to the drying chamber 69 and dried in a range of 140° C-160° C while being transported by the rollers 68.
  • the solid electrolyte membrane 62 which contains the solvent less than 3, wt.% is obtained.
  • the membrane thickness is continuously measured at the velocity of 600mm/min by using the electronic micrometer produced by Anritsu Corporation Ltd.
  • the data obtained by the measurement is recorded on a chart sheet with a 1/20 scale at the velocity of 30mm/min.
  • the data curves are measured by using a ruler. According to the measured value, average thickness and ⁇
  • a stress in the transportation direction of the membrane 62 (referred to as MDl) and that in the width direction (referred to as TDl) are measured to obtain elastic modulus when the membrane 62 is stretched for 0.5% with the tensile velocity of 10%/min. at 23° C and the humidity of 70% RH in the ambience.
  • Membrane cut by 15 mm x 250 mm is used as a sample.
  • the membrane is humidified for two hours at 23 0 C, and humidity of 65 % RH.
  • Tensile strength of the sample is calculated by using the Tensilon tester (a tensile testing machine) of model No. RTA- 100 produced by Orientech Corporation, Ltd. according to ISO 1184-1983.
  • the initial membrane length is 100 mm and the tensile speed is 200 ⁇ 5 mm/min.
  • the tensile strength of the membrane 62 is calculated by the initial tensile stress and the stretching.
  • a tensile strength value of a sample in the transportation direction is MD2 and that in the width direction is TD2. [4.
  • Ten measurement points are selected at intervals of Im along a lengthwise direction of the obtained solid electrolyte membrane. Each of ten measurement points is punched out as a disc-shaped sample with a diameter of 13mm. Each sample is interposed by two stainless steel plates. The proton conductivity thereof is measured by AC impedance method using 1470 and 1255B produced by Solartron Co., Ltd. The measurement is performed at 8O 0 C, and relative humidity of 95%. The proton ⁇
  • a fuel cell 141 is produced by using the membrane, and the output thereof is measured.
  • the producing method and the measurement method of the power density of the fuel cell 141 are described in the following.
  • catalyst membrane A used as the catalyst layers 132b, 133b 2 g of platinum-supporting carbon is mixed with 15 g of the solid electrolyte (5% DMF solution) , and dispersed for 30 minutes by using an ultrasonic disperser.
  • the average particle diameter of the resulting dispersion is about 500 nm.
  • the dispersion is applied onto the carbon paper with a thickness of 350 ⁇ m and dried. Thereafter, a disc-shape with a diameter of 9 mm is punched out of the carbon paper.
  • the catalyst membrane A is formed.
  • the above platinum supporting carbon is Vulcan XC72 with 50 wt . % platinum.
  • the solid electrolyte is the same as that in the membrane production.
  • the catalyst membrane A is attached to both surfaces of the solid electrolyte membrane such that the coated surfaces of the catalyst membrane A are attached the solid electrolyte membrane and heat-pressed at 80° C under 3MPa for 2 minutes .
  • the MEA 131 is formed.
  • the MEA 131 obtained in the above process (2) is set in the fuel cell shown in Fig. 7.
  • An aqueous 15 wt. % methanol solution is put into the fuel cell through an anode-side opening 151.
  • a cathode-side opening 152 is kept open to the air.
  • the anode 132 and the cathode 133 are connected via a multi-channel battery test system (1470) produced by Solartron g
  • a material B and the solvent are mixed by the following composition to dissolve the material B in the solvent to form a solid electrolyte dope 24 of 20 wt . % .
  • the dope 24 is referred to as a dope B.
  • the material B is sulfopropyl polyethersulfone with the sulfonation degree of 35%, and synthesized according to the synthesizing method disclosed in Japanese Patent Laid-Open Publication No. 2002-110174. Material B 100 pts . wt .
  • the dope B is used for producing the membrane 62.
  • the temperature of the air from the air blowers 91 to 93 is set at 80° C to 140 0 C. Inside the tenter device 64 is divided into three sections and the drying temperature is set at 140 0 C, 15O 0 C and
  • first and second liquids 65a and 66a of methanol and water at the ratio of 1 to 1 insulated at 60° C in the first and second liquid baths 65 and 66.
  • the membrane is dried in the drying chamber 69 in a range of 160° C and 180° C while being transported by plural rollers 68.
  • the solid electrolyte membrane 62 with the remaining solvent of less than
  • the membrane 62 is produced under the same conditions using 92 P2006/313918
  • the membrane 62 is produced under the same conditions using the same dope as those in the example 2 except that the width of the membrane 62 is stretched by 103% with respect to the membrane width inside the tenter device 64 prior to the stretching in the example 2.
  • the evaluation results of the obtained membrane are shown in Table 1.
  • Example 5 The compound shown in chemical formula 1 is used as the solid electrolyte.
  • the proton substitution that is, the acid processing to obtain the compound of the chemical formula 1 is performed in the membrane production process as described below instead of prior to the dope production.
  • a substance preceding the proton substitution that is, the precursor of the solid electrolyte is referred to as a material D.
  • the material D is dissolved in the solvent to form the dope for casting.
  • the dope is formed in the same manner as the dope 24 in the example 1.
  • the solvent is a mixture of the solvent 1 and the solvent 2.
  • the solvent 1 is a good solvent of the material D
  • the solvent 2 is a poor solvent of the material D.
  • the chemical formula 1 with the following composition is used: X is Na, Y is SO 2 , Z is (I) of the chemical formula 2, n is 0.33, m is 0.67, the number average molecular weight Mn is 61000, and the weight average molecular weight Mw is 159000.
  • Solvent component 1 (dimethyl sulfoxide) 256 pts. wt . ⁇ 6 313918
  • Solvent component 2 (methanol) 171 pts . wt .
  • the dope is cast onto the belt 82 and peeled off from the belt 82.
  • the peeled membrane is referred to as the precursor membrane since the membrane is formed of the material D.
  • the precursor membrane is subject to the same processes as those in the first example, and side edges of the precursor membrane are cut off by the edge slitting device 67.
  • the proton substitution is performed to the precursor membrane through acid processing.
  • the acid processing is to make the precursor membrane contact to the aqueous acid solution.
  • the structure of the precursor is changed to that shown in the chemical formula 1, that is, the solid electrolyte.
  • the aqueous acid solution is continuously supplied to the liquid bath and the membrane formed of the solid electrolyte is immersed in the aqueous acid solution.
  • the water is used for washing the membrane after the acid processing. After the washing, the membrane is transported to the drying chamber 69.
  • the evaluation results of the obtained membrane are shown in table 1. [Example 6]
  • a compound shown in the chemical formula 1 which is different from that used in the example 7 is used as the solid electrolyte.
  • the proton substitution for obtaining the compound of the chemical formula 1 is performed in the membrane production process instead of prior to the dope production in the same manner as the example 5.
  • the precursor used as the component of the dope is referred to as a material E.
  • the solvent is a mixture of the solvent component 1 and the solvent component 2 as shown below.
  • the solvent component 1 is a good solvent of the material E, and the solvent component 2 is a poor solvent of the material E.
  • the chemical formula 1 with the following composition is used: X is Na, Y is SO 2 , Z is (I) and (II) of the ⁇ 6 313918
  • n 0.33
  • m 0.67
  • the number average molecular weight Mn 68000
  • the weight average molecular weight Mw 200000.
  • (I) is 0.7 mol%
  • (II) is 0.3 mol%
  • Other conditions are the same as those in the example 5.
  • Solvent component 1 ( dimethylsulfoxide) 200 pts. wt .
  • Solvent component 2 (methanol) 135 pts. wt .
  • Example 7 The example 7 is carried out in the same manner as the example 5. In the example 7, after the washing, the casting membrane 24a is peeled off from the PET film to obtain the precursor membrane. After the washing, the membrane is immersed in the water at 30° C and then the water on the membrane is removed. [Example 8]
  • the membrane is produced under the same conditions as those in the example 7 except that the material D is changed to the material E.
  • solid electrolyte membrane is suitable for the solid electrolyte layer in the fuel cell .
  • the present invention enables to continuously produce the solid electrolyte membrane with excellent planarity and mechanical strength.
  • the obtained solid electrolyte membrane is suitably used for the solid electrolyte layer of the fuel cell.
PCT/JP2006/313918 2005-07-07 2006-07-06 Solid electrolyte membrane, method and apparatus for producing the same, membrane electrode assembly and fuel cell WO2007007819A1 (en)

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JP2006089808A JP2007042584A (ja) 2005-07-07 2006-03-29 固体電解質フィルム及びその製造方法、製造設備並びに燃料電池用電極膜複合体、及び燃料電池
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JP2005125705A (ja) * 2003-10-27 2005-05-19 Jsr Corp プロトン伝導性フィルムの製造法
JP2005171025A (ja) * 2003-12-09 2005-06-30 Jsr Corp プロトン伝導膜の製造方法

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US8802314B2 (en) 2008-10-17 2014-08-12 Toyota Jidosha Kabushiki Kaisha Reinforced electrolyte membrane for fuel cell, membrane-electrode assembly for fuel cell, and polymer electrolyte fuel cell comprising the same
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