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WO2006019029A1 - Membrane d'électrolyte de polymère, film de polymère comme matériau pour celle-ci, procédé de production de membrane d'électrolyte et pile à combustible en polymère solide utilisant ladite membrane d'électrolyte - Google Patents

Membrane d'électrolyte de polymère, film de polymère comme matériau pour celle-ci, procédé de production de membrane d'électrolyte et pile à combustible en polymère solide utilisant ladite membrane d'électrolyte Download PDF

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Publication number
WO2006019029A1
WO2006019029A1 PCT/JP2005/014730 JP2005014730W WO2006019029A1 WO 2006019029 A1 WO2006019029 A1 WO 2006019029A1 JP 2005014730 W JP2005014730 W JP 2005014730W WO 2006019029 A1 WO2006019029 A1 WO 2006019029A1
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Prior art keywords
polymer
electrolyte membrane
polymer electrolyte
fuel cell
polymer film
Prior art date
Application number
PCT/JP2005/014730
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English (en)
Japanese (ja)
Inventor
Hidekazu Kuromatsu
Tomokazu Yamane
Original Assignee
Kaneka Corporation
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Publication date
Application filed by Kaneka Corporation filed Critical Kaneka Corporation
Priority to JP2006531721A priority Critical patent/JP4995568B2/ja
Publication of WO2006019029A1 publication Critical patent/WO2006019029A1/fr

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    • 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
    • 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
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1088—Chemical modification, e.g. sulfonation
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a polymer electrolyte membrane, a polymer film as a material thereof, a method for producing the electrolyte membrane, and a solid polymer fuel cell using the electrolyte membrane.
  • Polymer compounds containing proton conductive groups such as sulfonic acid groups are solid polymer fuel cells, direct liquid fuel cells, direct methanol fuel cells, humidity sensors, gas sensors, and electochromic display elements. Used as a raw material for electrochemical devices such as
  • polymer electrolyte fuel cells are expected as one of the pillars of new energy technology.
  • Solid polymer fuel cells using a polymer electrolyte membrane made of a polymer compound containing a proton-conducting group have features such as operation at a low temperature and small size and light weight.
  • Direct liquid fuel cells, especially direct methanol fuel cells that use methanol directly as a fuel have features such as a simple structure and ease of fuel supply and maintenance, as well as high energy density.
  • lithium-ion secondary batteries it is expected to be applied to small consumer portable devices such as mobile phones and notebook computers.
  • Polymer compounds containing proton-conducting substituents such as sulfonic acid groups include solid polymer fuel cells, direct liquid fuel cells, direct methanol fuel cells, humidity sensors, gas sensors, and electochromic. Used as a raw material for electrochemical elements such as display elements. Among these, polymer electrolyte fuel cells are expected as one of the pillars of new energy technology.
  • a solid polymer fuel cell that uses an electrolyte membrane made of a polymer compound having a proton-conducting substituent is an automatic sensor that can operate at low temperatures and is small and lightweight.
  • Application to mobile vehicles such as cars, home cogeneration systems, and small portable devices for consumer use is under consideration.
  • Direct liquid fuel cells, particularly direct methanol fuel cells that use methanol as the direct fuel have features such as a simple structure, ease of fuel supply and maintenance, and high energy density. As a replacement for the next battery, it is expected to be applied to small consumer portable devices such as mobile phones and laptop computers.
  • a perfluorocarbon sulfonic acid membrane represented by Nafion has been widely studied.
  • Perfluorocarbon sulfonic acid membranes have high proton conductivity and are excellent in chemical stability such as acid resistance and acid resistance.
  • naphthion registered trademark
  • a so-called chemical short reaction occurs in which the permeation (also referred to as crossover) of a hydrogen-containing liquid such as methanol, which is a raw material for direct liquid fuel cells, is large.
  • Proton conductive electrolyte membranes used in polymer electrolyte fuel cells include naphthion ions.
  • Perfluorocarbon sulfonic acid membranes represented by (Nafion) (registered trademark) have been widely studied. Perfluorocarbon sulfonic acid membranes have high proton conductivity and excellent chemical stability such as acid resistance and acid resistance.
  • Nafion registered trademark
  • Nafion has a disadvantage that it is very expensive because it uses a complicated manufacturing process in which raw materials used are high.
  • naphthion registered trademark
  • Patent Document 1 proposes a sulfonic acid group-containing polyphenylene sulfide that is soluble in an aprotic polar solvent. It is disclosed that by introducing a sulfonic acid group in a chlorosulfonic acid homogeneous solution of poly (phenylene sulfide), solubility in an aprotic polar solvent can be imparted and the film can be easily covered.
  • solubility in methanol which is considered as a fuel for a fuel cell, may be imparted at the same time, and the range of use is remarkably restricted.
  • chlorosulfonic acid is used as a solvent and a sulfonating agent, it is difficult to control the amount of sulfonic acid group introduced or it may cause deterioration of the polysulfide sulfide.
  • a large amount of acid waste liquid is discharged at the time of reaction, at the time of collecting the resin, and at the time of washing.
  • suppressing permeation also called crossover
  • Patent Document 2 discloses a method for producing a polymer electrolyte membrane (proton conductive polymer membrane) made of a sulfonic acid group-containing polysulfide sulfide. According to this method, a polymer electrolyte membrane made of a solvent-insoluble sulfonic acid group-containing polyphenylene sulfide can be obtained. Well, it ’s been cunning.
  • Patent Document 3 discloses a polymer electrolyte membrane obtained by a method in which a polymer porous support is filled with an electrolyte monomer to increase the molecular weight.
  • Patent Document 4 discloses a polymer electrolyte membrane obtained by a method of introducing a sulfonic acid group into a polymer porous support having a high molecular weight by filling with a monomer. These are said to suppress the permeation (crossover) of the fuel and methanol used as fuel because they are suppressed by the porous support.
  • the manufacturing process is complicated, it is easily assumed that there will be problems in terms of manufacturing cost and productivity.
  • Patent Document 3 discloses a polymer electrolyte membrane in which a polymer porous support is filled with an electrolyte monomer to increase the molecular weight. Meta used as fuel It is said that the permeation (crossover) of these materials is suppressed because swelling with respect to knoll and water is suppressed by the porous support.
  • the manufacturing process is complicated, there are problems in terms of manufacturing costs.
  • Patent Document 1 Japanese Patent Publication No. 11 510198
  • Patent Document 2 Pamphlet of International Publication No. 02Z062896
  • Patent Document 3 Republished WO00Z54531
  • Patent Document 4 Japanese Patent Laid-Open No. 2005-5171
  • the object of the present invention has been made in view of the above problems, and has excellent proton conductivity useful as a constituent material for polymer electrolyte fuel cells, direct liquid fuel cells, and direct methanol fuel cells.
  • the first of the present invention is
  • the third of the present invention is (A) is selected from the group consisting of polystyrene, syndiotactic polystyrene, polyphenylene ether, modified polyphenylene ether, polysulfone, polyethersulfone, polyetherolene ketone and polyphenylene sulfide, and derivatives thereof.
  • 1 4 3 3 3 4 9 is selected from the group consisting of:
  • a sixth aspect of the present invention is
  • the above-mentioned) is at least one selected from polyethylene, polypropylene, and polymethylpentene, and the group force that is also a derivative force thereof.
  • (C) is polystyrene or a polystyrene derivative
  • R ⁇ is C H, and R ⁇ are independent of each other and are the same or different.
  • Said (C) is polystyrene polyisobutylene-polystyrene triblock copolymer, polystyrene poly (ethylene Z propylene) block copolymer, polystyrene poly (ethylene Z propylene) -polystyrene triblock copolymer, polystyrene-poly (ethylene Z).
  • (Butylene) polystyrene triblock copolymer and polystyrene poly (ethylene ether) The polymer according to any one of (2) to (7), characterized in that it is at least one selected from the group force consisting of (len) Z-propylene) -polystyrene triblock copolymer and derivatives thereof.
  • polymer electrolyte membrane has a methanol permeability coefficient of 2, OOO ⁇ mol / Ccm-day) or less for a 64 wt% aqueous methanol solution at 25 ° C.
  • a method for producing a polymer electrolyte membrane for use in a solid polymer fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell, wherein the polymer according to any one of (1) to (10) above A method for producing a polymer electrolyte membrane, comprising contacting the film with a sulfonating agent in the presence of an organic solvent;
  • the twentieth aspect of the present invention is The halogenated hydrocarbon power dichloromethane, 1,2-dichloromouth ethane, and the group power of 1 chlorobutane power is at least one selected, and V of (17) to (19) A method for producing the polymer electrolyte membrane according to
  • a direct liquid fuel cell characterized in that
  • a direct methanol fuel cell characterized in that
  • (1) to (23) are the following (A-1) to (A-15), (B-1) to (B-13), (C1) to (C1)
  • thermoplastic elastomer (A) a polymer compound having an aromatic unit, (B) a thermoplastic elastomer,
  • A-2 of the present invention is
  • (A) is selected from the group consisting of polystyrene, syndiotactic polystyrene, polyphenylene ether, modified polyphenylene ether, polysulfone, polyethersulfone, polyetherolene ketone and polyphenylene sulfide, and derivatives thereof.
  • the polymer phenolic as described in item (A-1) of the present invention characterized in that it is at least one selected.
  • this film As a material, it is preferable to realize a polymer electrolyte membrane in view of its high chemical and thermal stability and easy introduction of proton conductive groups.
  • Said (B) is a copolymer of polystyrene or a polystyrene derivative and the following general formula (2) and Z or (3): (A-1) to (A-2) of the present invention, A polymer film according to any one of
  • R ⁇ is C H, and R ⁇ may be the same or different from each other.
  • n, n, and x are integers of 0 or more.
  • this film As a material, it is preferable to realize a polymer electrolyte membrane in view of excellent processability and easy introduction of proton conductive groups.
  • polystyrene-polyisobutylene-polystyrene triblock copolymer polystyrene poly (ethylene Z propylene) block copolymer, polystyrene poly (ethylene Z propylene) -polystyrene triblock copolymer, polystyrene-poly (ethylene Z block).
  • Tylene Polystyrene triblock copolymer and polystyrene poly (ethylene-ethylene Z-propylene) -polystyrene triblock copolymer, and their at least one selected from the group force consisting of derivatives thereof.
  • A-1) to (A-3) the polymer film according to any of the above,
  • this film improves the compatibility and dispersibility of each component. It is preferable in that it has excellent processability and mechanical properties and is easy to introduce proton conductive groups.
  • V ⁇ Polymer electrolyte membrane can be realized.
  • the above (C) is at least one selected from polymer compounds having the following general formula (1): (A-1) to (A-4) of the present invention, A polymer Finolem as described in
  • this film By using this film as a material, a polymer electrolyte membrane having high chemical stability and excellent methanol blocking properties as described below can be realized.
  • the polymer film of the present invention described in the above (A-1) to (A-7) is a polymer used for a solid polymer fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell. It is suitably used as a material for the electrolyte membrane.
  • the (A-8) of the present invention is
  • the present invention is a high polymer used for solid polymer fuel cells, direct liquid fuel cells, and direct methanol fuel cells.
  • the present invention relates to a molecular electrolyte membrane and a polymer film which is a material of the polymer electrolyte membrane.
  • the polymer electrolyte membrane of the present invention has at least three kinds of polymer compound powers of a polymer compound having an aromatic unit, a thermoplastic elastomer, and a polymer compound having no aromatic unit, and has an excellent proton. Both conductivity and high methanol barrier properties can be achieved.
  • the polymer compound having an aromatic unit includes polystyrene, syndiotactic polystyrene, polyphenylene ether, modified polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, and polyphenylene sulfide.
  • at least one selected from the group consisting of these derivatives is preferable because of high chemical and thermal stability and easy introduction of proton conductive groups.
  • thermoplastic elastomer is a copolymer of polystyrene or a polystyrene derivative and the following general formula (2) and Z or (3)
  • the obtained polymer film and polymer electrolyte membrane It is preferable because it is excellent in processability and mechanical properties and is easy to introduce a proton conductive group.
  • R ⁇ is C H, and R ⁇ may be the same as or different from each other.
  • n, n, and x are integers of 0 or more.
  • thermoplastic elastomer polystyrene, polyisobutylene, polystyrene, triblock copolymer, polystyrene-poly (ethylene Z propylene) block copolymer, polystyrene, poly (ethylene Z propylene), polystyrene triblock copolymer, polystyrene Poly (ethylene Z butylene) polystyrene triblock copolymer and polystyrene Poly (ethylene ethylene Z propylene) polystyrene triblock copolymer, and at least one selected from the group consisting of derivatives thereof, each component If the compatibility and dispersibility of the resin is improved, the processability and mechanical properties are excellent, and the sulfonic acid group can be easily introduced, this is preferable.
  • the polymer compound having no aromatic unit is at least one selected from the following general formula (1) because of high chemical stability and excellent methanol blocking properties. [0063] [Chemical 8]
  • the polymer compound having no aromatic unit is polyethylene, Z, or polypropylene because it has high chemical stability and excellent methanol barrier properties, and can be produced at low cost.
  • the polymer compound is contained in an amount of 40% by weight or more and 90% by weight or less without an aromatic unit, since both excellent proton conductivity and high methanol blocking property are compatible.
  • the proton conductive group is preferably a sulfonic acid group from the viewpoint of easy introduction of the proton conductive group and proton conductivity of the obtained polymer electrolyte membrane.
  • the method for producing a polymer film comprising producing the polymer film according to any one of
  • (A-12) of the present invention is The method for producing a polymer electrolyte membrane according to (A-11) of the present invention, wherein the sulfonating agent is chlorosulfonic acid,
  • the present invention further relates to a high polymer used for a polymer electrolyte fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell.
  • the present invention relates to a method for producing a molecular electrolyte membrane and a method for producing a polymer film that is a material of a polymer electrolyte membrane. By producing the polymer film by melt extrusion, a polymer film material suitable for obtaining a polymer electrolyte membrane can be obtained with high productivity.
  • a high-molecular electrolyte membrane that achieves both excellent proton conductivity and high methanol barrier properties can be produced easily and with high production. It is preferable because it is obtained.
  • the sulfonating agent has a strong S-chlorosulfonic acid because a polymer electrolyte membrane having high proton conductivity can be easily obtained as soon as a sulfonic acid group as a proton conductive group is introduced.
  • a polymer electrolyte fuel cell characterized in that
  • a direct liquid fuel cell characterized in that
  • polymer electrolyte membrane according to any one of (A-8) or (A-9) of the present invention, or any of (A-11) or (A-12) of the present invention Listed polymer A polymer electrolyte membrane obtained by a method for producing a denatured membrane,
  • the polymer electrolyte membrane of the present invention or the polymer electrolyte membrane obtained by the production method of the present invention is further provided.
  • the direct polymer electrolyte fuel cell used is excellent as a polymer electrolyte fuel cell because it has excellent proton conductivity and high durability.
  • the direct liquid fuel cell using the polymer electrolyte membrane of the present invention or the polymer electrolyte membrane obtained by the production method of the present invention has excellent proton conductivity and high liquid fuel barrier properties. It is excellent as a direct liquid fuel cell.
  • the direct methanol fuel cell using the polymer electrolyte membrane of the present invention or the polymer electrolyte membrane obtained by the production method of the present invention has excellent proton conductivity and high! It is compatible as a direct methanol fuel cell.
  • a material for a polymer electrolyte membrane used in a polymer electrolyte fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell at least,
  • Said (A) is polystyrene, syndiotactic polystyrene, polyphenylene ether, modified polyphenylene ether, polysulfone, polyether sulfone, polyetherolene ketone and polyphenylene sulfide, and derivatives or copolymers thereof.
  • the (B-1) of the present invention is characterized in that at least one kind of group force is selected.
  • this film As a material, it is preferable to realize a polymer electrolyte membrane from the viewpoints of high chemical and thermal stability and easy introduction of proton conductive groups.
  • this film By using this film as a material, a polymer electrolyte membrane having high chemical stability and excellent methanol blocking properties as described below can be realized.
  • the polymer film of the present invention described in the above (B-1) to (B-5) of the present invention is used for a solid polymer fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell.
  • High minute It is suitably used as a material for the child electrolyte membrane.
  • the polymer electrolyte membrane according to the sixth aspect of the present invention wherein the proton conductive group is a sulfonic acid group,
  • the present invention is a high polymer used for a polymer electrolyte fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell.
  • the present invention relates to a polymer electrolyte membrane and a polymer film which is a material of a polymer electrolyte membrane.
  • the polymer electrolyte membrane of the present invention has at least two kinds of polymer compound forces, ie, a polymer compound having an aromatic unit and a polymer compound having no aromatic unit.
  • the polymer compound having the aromatic unit includes polystyrene, syndiotactic polystyrene, polyphenylene ether, modified polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, and polyphenylene sulfide.
  • at least one selected from the group consisting of derivatives and copolymers thereof is preferred because it has high chemical and thermal stability and facilitates the introduction of proton conductive groups.
  • polymer compound having no aromatic unit is at least one selected from polymer compounds represented by the following general formula (1), methanol-blocking property with high chemical stability Is preferable because it is excellent. [0088] [Chemical 10]
  • 1-4 may be the same or different from each other.
  • the polymer compound having no aromatic unit is polyethylene, Z, or polypropylene because the chemical stability is high, the methanol blocking property is excellent, and the polymer can be produced at low cost.
  • the polymer compound is contained in an amount of 40% by weight or more and 90% by weight or less without an aromatic unit, it is particularly preferable since both excellent proton conductivity and high methanol blocking properties are achieved.
  • the proton conductive group is preferably a sulfonic acid group from the viewpoint of ease of introduction of the proton conductive group and proton conductivity of the obtained polymer electrolyte membrane.
  • the method for producing a polymer film comprising producing the polymer film according to any one of
  • (B-10) of the present invention is The method for producing a polymer electrolyte membrane according to (B-9) of the present invention, wherein the sulfonating agent is chlorosulfonic acid,
  • the present invention further includes a high polymer used for a polymer electrolyte fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell.
  • the present invention relates to a method for producing a molecular electrolyte membrane and a method for producing a polymer film that is a material of the polymer electrolyte membrane. By producing the polymer film by melt extrusion, a polymer film material suitable for obtaining a polymer electrolyte membrane can be obtained with high productivity.
  • a polymer electrolyte membrane that achieves both excellent proton conductivity and high methanol barrier properties can be obtained with high productivity. Obtained and preferred.
  • the sulfonating agent is chlorosulfonic acid because a polymer electrolyte membrane having high proton conductivity is easily obtained as soon as a sulfonic acid group as a proton conductive group is introduced.
  • (B-11) of the present invention is (B-11)
  • polymer electrolyte membrane according to any one of (B-6) and (B-7) of the present invention, or any one of (B-9) or (B-10) of the present invention A polymer electrolyte membrane obtained by the method for producing a polymer electrolyte membrane according to claim 1,
  • a polymer electrolyte fuel cell characterized in that
  • polymer electrolyte membrane according to any one of (B-6) and (B-7) of the present invention, or any one of (B-9) or (B-10) of the present invention A polymer electrolyte membrane obtained by the method for producing a polymer electrolyte membrane according to claim 1,
  • a direct liquid fuel cell characterized in that
  • the polymer electrolyte membrane according to any one of (B-6) and (B-7) of the present invention, or any one of (B-9) or (B-10) of the present invention The polymer electrolysis described A polymer electrolyte membrane obtained by a method for producing a membrane,
  • the polymer electrolyte membrane of the present invention or the polymer electrolyte membrane obtained by the production method of the present invention is further used.
  • the direct solid polymer fuel cell is excellent as a solid polymer fuel cell because it has excellent proton conductivity and high durability.
  • the direct liquid fuel cell using the polymer electrolyte membrane of the present invention or the polymer electrolyte membrane obtained by the production method of the present invention has excellent proton conductivity and high liquid fuel blocking properties. Therefore, it is excellent as a direct liquid fuel cell.
  • the direct methanol fuel cell using the polymer electrolyte membrane of the present invention or the polymer electrolyte membrane obtained by the production method of the present invention has excellent proton conductivity and high methanol barrier properties. It is compatible as a direct methanol fuel cell.
  • the aliphatic polymer compound has the following formulas (4) to (6):
  • Any of atomic groups selected from 3 3 3 4 9, and X and Y may be the same or different from each other. )
  • the aromatic polymer compound is at least one of polyphenylene sulfide, polyphenylene ether, polystyrene, syndiotactic polystyrene, polyether sulfone, polyether ether ketone (C-1)
  • a polymer film according to any one of (C-3) is at least one of polyphenylene sulfide, polyphenylene ether, polystyrene, syndiotactic polystyrene, polyether sulfone, polyether ether ketone (C-1)
  • the polymer film of the present invention described above is suitably used as a material for a polymer electrolyte membrane used for a solid polymer fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell.
  • a proton-conducting polymer electrolyte membrane for use in a polymer electrolyte fuel cell, a direct liquid fuel cell, or a direct methanol fuel cell, and any one of (C-1) to (C-4) A polymer electrolyte membrane characterized in that a proton conductive group is bonded to an aromatic polymer compound present in the polymer film described above,
  • the present invention relates to a polymer electrolyte membrane used for a solid polymer fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell.
  • the polymer electrolyte membrane of the present invention has at least two kinds of polymer compound forces, that is, an aliphatic polymer compound and an aromatic polymer compound containing a proton-conducting group. High methanol barrier properties.
  • the aliphatic polymer compound is contained in the polymer electrolyte membrane in an amount of 10% by weight to 95% by weight because both excellent proton conductivity and high methanol blocking properties are achieved.
  • the aliphatic polymer compound has the following formulas (4) to (6):
  • X and Y are ⁇ , CH, Cl, F, OCOCH, CN, COOH, COOCH, OC H, or
  • Any of atomic groups selected from 3 3 3 4 9, and X and Y may be the same or different from each other. And at least one selected from an aliphatic polymer compound having a repeating unit represented by formula (1) as a constituent component because it has excellent chemical and thermal stability and processability. It is preferable because it is available.
  • X in formula (4) is H, CH, Cl, F, and X and Y in formula (5) are ( ⁇ ,
  • F and X in formula (6) are at least one selected from aliphatic polymer compounds having a repeating unit represented by F or H as a constituent, particularly chemically and thermally stable. Sex, processing
  • the aromatic polymer compound is at least one of polyphenylene sulfide, polyphenylene ether, polystyrene, syndiotactic polystyrene, polyether sulfone, and polyether ether ketone
  • Prototype with high thermal stability Since it is easy to introduce a conductive group, it is preferable because it is a membrane having high proton conductivity, and high methanol barrier properties.
  • the proton-conductive substituent is preferably a sulfonic acid group from the viewpoint of ease of introduction of the proton-conductive substituent and proton conductivity of the resulting proton-conductive polymer electrolyte membrane. .
  • the contact with the sulfonating agent is carried out in an organic solvent (C-7) to (
  • the halogenated hydrocarbon compound is 1-chlorobutane (C-10).
  • the present invention further provides a polymer having at least two kinds of polymer compounds, ie, an aliphatic polymer compound and an aromatic polymer compound.
  • the present invention relates to a method for producing a polymer electrolyte membrane in which a film is brought into contact with a sulfonating agent. This manufacturing method and By doing so, it becomes a method for producing a polymer electrolyte membrane with high productivity.
  • the method for producing a polymer electrolyte membrane of the present invention when the aliphatic polymer compound is contained in an amount of 10% by weight to 95% by weight in the polymer film, the obtained polymer electrolyte membrane is obtained. It is preferable because it has both excellent proton conductivity and high methanol blocking property.
  • the aliphatic polymer compound is represented by the following formulas (4) to (6):
  • Any of atomic groups selected from 3 3 3 4 9, and X and Y may be the same or different from each other. )
  • At least one selected from the aliphatic polymer compounds having a repeating unit represented by the formula is excellent in chemical and thermal stability and processability, it is also inexpensive. Favorable because it is industrially available.
  • X in the formula (4) is H, CH, Cl, F, and X and Y in the formula (5) are (
  • X is at least one selected from aliphatic polymer compounds having a repeating unit represented by F, H as a constituent component. It is preferable because it is excellent in mechanical and thermal stability and processability, and is industrially available at a low cost.
  • the aromatic polymer compound is an aromatic polymer compound because it is commercially available at low cost. Further, when the aromatic polymer compound is at least one of polyphenylene sulfide, polyphenylene ether, polystyrene, syndiotactic polystyrene, polyether sulfone, polyether ether ketone, It is preferable because a proton-conductive group having high stability can be easily introduced, so that it becomes a membrane having high proton conductivity and higher methanol blocking property.
  • the method for producing a polymer electrolyte membrane of the present invention when the sulfonating agent power is chlorosulfonic acid, sulfonating can be performed in a short time, and the production method of a proton-conducting polymer electrolyte with low production cost is possible. I prefer U ⁇ .
  • the method for producing a proton conductive polymer electrolyte membrane of the present invention when the contact with the sulfonating agent is carried out in an organic solvent, a sulfonative reaction can be carried out uniformly, and a membrane having high mechanical strength is preferred.
  • the organic solvent is a halogenated hydrocarbon-based compound
  • it can be industrially obtained at a low cost, which is preferable as a method for manufacturing a polymer electrolyte membrane at a low manufacturing cost.
  • the halogenated hydrocarbon-based compound is 1 chlorobutane because the obtained proton-conducting polymer electrolyte membrane has both excellent proton conductivity, high properties, and methanol blocking property.
  • the direct liquid fuel cell is a direct methanol fuel cell, the direct liquid fuel cell according to (C13),
  • the polymer electrolyte membrane of the present invention As shown in the above (C-12) to (C-14), the polymer electrolyte membrane of the present invention, a certain ⁇ , is a solid using the polymer electrolyte membrane obtained by the production method of the present invention.
  • Polymer fuel cells are excellent as solid polymer fuel cells because they have high proton conductivity and high durability.
  • direct liquid fuel cells using the polymer electrolyte membrane of the present invention or the polymer electrolyte membrane obtained by the production method of the present invention have a high proton conductivity and a high liquid fuel barrier property. Therefore, it is excellent as a direct liquid fuel cell.
  • the direct methanol fuel cell using the polymer electrolyte membrane of the present invention or the polymer electrolyte membrane obtained by the production method of the present invention has a high proton conductivity and a high methanol blocking property. Excellent as a methanol fuel cell! / Speak.
  • a polymer electrolyte membrane having at least two kinds of compound power that is, an aliphatic polymer compound and an aromatic polymer compound containing a proton conductive group. It became possible to express a high methanol barrier property. These have excellent proton conductivity and high methanol barrier properties, and are useful as polymer electrolyte membranes for polymer electrolyte fuel cells, direct liquid fuel cells, and direct methanol fuel cells. Further, the polymer electrolyte membrane can be realized by using the polymer film of the present invention as a material.
  • At least three polymer compounds including a polymer compound having an aromatic unit, a thermoplastic elastomer, and a polymer compound having no aromatic unit are included as essential components.
  • High molecular electrolyte membranes in which proton conductive groups are introduced into aromatic units in polymer films, have excellent proton conductivity and high methanol barrier properties, such as solid polymer fuel cells and direct liquid fuels. It is useful as a polymer electrolyte membrane for batteries and direct methanol fuel cells. Further, by using the polymer film of the present invention as a material, It became possible to realize a molecular electrolyte membrane.
  • At least two kinds of polymer compounds, a polymer compound having an aromatic unit, and a polymer compound having no aromatic unit are included,
  • the derivative means that at least one of hydrogen atoms that can be substituted in the basic compound is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, A compound substituted with a substituent such as a hydroxyl group, a carbonyl group, a carboxyl group, an ether group, an ester group, an acyl group or an amino group.
  • the copolymer may be any of a block copolymer and a random copolymer.
  • the polymer electrolyte of the present invention and the polymer film of the material preferably include a polymer compound having an aromatic unit.
  • a proton conductive group such as a sulfonic acid group can be substituted for the aromatic unit contained in the polymer compound, and when the polymer electrolyte membrane is formed, the proton conductivity can be expressed.
  • the polymer compound having an aromatic unit include polystyrene, syndiotactic polystyrene, polyaryl ether sulfone, polyether ether sulfone, polyether ether ketone, polyether ether ketone, polysulfone, polyparaphenylene, and polyphenylene.
  • Rensulfide polyphenylene ether, modified polyphenylene ether, polyphenylene sulfoxide, polyphenylene sulfide sulfone, polyphenylene sulfone, polybenzimidazole, polybenzoxazole, polybenzothiazole, polyethersulfone, Poly 1, 4 Biff Examples include ether ether sulfone, polyarylene ether sulfone, polyimide, polyether imide, cyanate ester resin, and polyether ether ketone. In addition, derivatives and copolymers thereof are also within the scope of the present invention.
  • compatibility and dispersibility with other polymer compound components ease of introduction of proton-conducting groups, and handling properties of the resulting polymer film, Furthermore, in consideration of proton conductivity, methanol blocking property, chemical 'thermal stability, etc. of the polymer electrolyte obtained therefrom, polystyrene, syndiotactic polystyrene, polyphenylene ether, modified polyphenylene ether, polysulfone It is preferably at least one selected from the group strength of polyethersulfone, polyetheretherketone and polyphenylene sulfide, and derivatives and copolymers thereof.
  • the copolymer of the high molecular compound include a copolymer of polystyrene or a polystyrene derivative and the following general formula (2) and Z or (3).
  • the polymer electrolyte of the present invention and the polymer film of the material preferably include a thermoplastic elastomer.
  • the presence of the thermoplastic elastomer improves the compatibility and dispersibility with other polymer compound components and, as a result, improves the film properties, etc., and the mechanical strength of the polymer film and polymer electrolyte membrane of the present invention. Nyanoding performance is improved, which is preferable
  • thermoplastic elastomer used in the present invention is preferably a copolymer of a polystyrene or polystyrene derivative and the following general formula (2) and Z or (3).
  • R ⁇ is C H, and R ⁇ may be the same or different from each other.
  • n, n, and x are integers of 0 or more.
  • polystyrene or polystyrene derivatives having aromatic units are excellent in compatibility with the polymer compound having the aromatic units.
  • other components do not have aromatic units, they are preferably excellent in compatibility with high molecular compounds having no aromatic units, which will be described later.
  • polystyrene polyisobutylene polystyrene triblock copolymer Polystyrene poly (ethylene Z propylene) block copolymer, polystyrene monopoly (ethylene Z propylene) monopolystyrene triblock copolymer, polystyrene poly (ethylene Z butylene) polystyrene triblock copolymer and polystyrene poly (ethylene ethylene Z) Propylene) polystyrene triblock copolymers, and at least one selected from the group consisting of derivatives thereof Preferred to be a seed. Since these components have a block unit without an aromatic unit, they are preferably excellent in compatibility with a polymer compound having no aromatic unit, which will be described later.
  • the polymer electrolyte of the present invention and the polymer film of the material thereof preferably contain a polymer compound having no aromatic unit. Since there is no aromatic unit in these structures, proton conductive groups such as sulfonic acid groups are not introduced into the aromatic unit. Therefore, the polymer electrolyte membranes obtained from these have hydrophilic proton conductive groups such as sulfonic acid groups introduced into the aromatic units of other polymer compounds! It is difficult to swell, and a polymer electrolyte membrane having a high methanol barrier property can be obtained.
  • Examples of the polymer compound having no aromatic unit that can be used in the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl 1-butene, and 4-methyl 1 Polyolefin resins such as pentene, 5-methyl-1-heptene homopolymers or copolymers such as polyolefin resin, polychlorinated bulu, salt-vinyl bis-acetate vinyl copolymer, salt hydruvyl monosalt hibilidene Polymers, salt-based resin such as salt-hybryl 1-year-old refin copolymer, polyamide resin such as nylon 6 and nylon 66, polytetrafluoroethylene, tetrafluoroethylene perfluoroalkyl vinyl ether Polymer, Tetrafluoroethylene Exafluoropropylene Copolymer, Tetrafluoroethylene Ethylene Copolymer Ruoroechiren, polyvinylidene off Ruoraido,
  • the polymer compound is preferably a polymer compound represented by the following general formula (1).
  • the content of the polymer compound having no aromatic unit is preferably 40 wt% or more and 90 wt% or less. If the content is less than 40% by weight, the polymer electrolyte membrane is not sufficiently effective in suppressing swelling of the polymer electrolyte membrane with water or methanol aqueous solution, and the desired methanol barrier property may not be exhibited. On the other hand, if the amount is more than 90% by weight, the amount of the polymer compound having an aromatic unit capable of introducing a proton conductive group becomes too small, and there is a possibility that desired proton conductivity may be exhibited.
  • any material that dissociates protons in a water-containing state can be used.
  • the power that can be exemplified by sulfonic acid group, phosphoric acid group, carboxylic acid group, phenolic hydroxyl group and the like is not limited to these.
  • a sulfonic acid group is preferable.
  • the ion exchange capacity of the polymer electrolyte derived from the content of the proton conductive group is preferably 0.3 meq Zg or more, and more preferably 0.5 meq Zg or more. If the ion exchange capacity is lower than 0.3 milliequivalent Zg, the desired proton conductivity may not be exhibited, which is not preferable.
  • the proton-conductive substituent contained in the proton-conductive polymer electrolyte of the present invention can be used as long as it dissociates protons in a water-containing state.
  • the power that can be exemplified by sulfonic acid group, phosphoric acid group, carboxylic acid group, phenolic hydroxyl group and the like is not limited to these.
  • a sulfonic acid group is preferable.
  • the ion exchange capacity of the proton conducting polymer electrolyte derived from the content of the proton conducting substituent is
  • it is 0.3 meq Zg or more, more preferably 0.5 meq Zg or more. If the ion exchange capacity is lower than 0.3 milliequivalent Zg, the desired proton conductivity may not be exhibited, which is not preferable.
  • a known method can be used to obtain a polymer film.
  • melt extrusion molding such as inflation method and T-die method, calendar method, casting method, cutting method, emulsion method, and hot press method.
  • a treatment such as biaxial stretching in order to control the molecular orientation or the like, or a heat treatment to control the crystallinity.
  • a known method can be used to obtain a polymer film.
  • a polymer film for example, a high molecular film
  • Those obtained by the inflation method, T-die method, calendar method, cast method, cutting method, emulsion method, hot press method, etc. can be used. Further, a treatment such as biaxial stretching may be performed to control the molecular orientation or the like, or a heat treatment may be performed to control the crystallinity.
  • a polymer compound having an aromatic unit which is a main raw material of the polymer film, a thermoplastic elastomer, and a polymer compound having no aromatic unit.
  • Pellet and powder are mixed in advance at the specified blending ratio and put into the extruder set with ⁇ die.
  • a method of forming a film while melt kneading can be applied.
  • Pellet and powder are mixed in advance at the specified blending ratio and put into the extruder set with ⁇ die.
  • a method of forming a film while melt kneading can be applied.
  • the extruder used is a twin screw extruder, a polymer film in which these components are melted and uniformly dispersed can be obtained.
  • the film may be formed using pellets melt-kneaded with a twin-screw extruder so as to obtain a predetermined blending ratio in advance, or a masterbatch pellet may be used to achieve a predetermined blending ratio. It may be formed into a film while being melt-kneaded.
  • the film may be formed with a single-screw extruder with a T-die set.
  • the thickness of the polymer film of the present invention any thickness can be selected depending on the application. In consideration of reducing the internal resistance of the polymer electrolyte membrane obtained from the polymer film of the present invention, the thinner the polymer film, the better. On the other hand, in view of methanol blocking property and nanoring property of the obtained polymer electrolyte membrane, it is not preferable that the polymer film is too thin. In view of these, the thickness of the polymer film is preferably 1.2 / ⁇ ⁇ to 350 m. If the thickness of the polymer film is less than 1.2 m, it is difficult to form a film, and it is likely to become wrinkled at the time of processing when a proton conductive group is introduced or dried, and damage may occur. There is a risk that handling will be significantly reduced. If the thickness of the polymer film exceeds 350 m, the proton conductivity of the obtained polymer electrolyte membrane may be manifested.
  • the polymer film of the present invention comprises at least a polymer compound having an aromatic unit and an aromatic unit, and a polymer compound, wherein the aromatic unit is not! It is preferable that the polymer compound has a structure in which a polymer compound having an aromatic unit is dispersed in the polymer compound. It is difficult to introduce hydrophilic proton-conducting groups represented by sulfonic acid groups! ⁇ No aromatic units ⁇ Swelling of polymer electrolyte membranes against hydrogen-containing liquids such as water and methanol is suppressed It is possible to exhibit excellent methanol barrier properties.
  • the dispersion state is not particularly limited. ⁇ 10m sea island structure (structure without aromatic unit, polymer compound is ⁇ sea '', polymer compound with aromatic unit is ⁇ island '') or layer structure of ⁇ m order It can be enumerated as an example of a preferable form.
  • the swelling suppression effect of the polymer compound without the aromatic unit may be reduced.
  • the dispersion state of the polymer compound having an aromatic unit is extremely poor, there is a possibility that proton conductivity may be insufficient or methanol blocking property may be insufficient when a polymer electrolyte membrane is obtained. .
  • the above-described polymer film is contacted with a sulfonating agent in the presence of an organic solvent.
  • a sulfonating agent in the presence of an organic solvent.
  • sulfonating agents examples include known sulfonating agents such as chlorosulfonic acid, fuming sulfuric acid, sulfur trioxide, sulfur trioxide, sulfur triethyl phosphate, concentrated sulfuric acid, and trimethylsilyl chloride sulfate. It is preferable to illustrate. Considering the ease of industrial availability, the ease of introduction of sulfonic acid groups, and the properties of the resulting polymer electrolyte membrane, chlorosulfonic acid is preferred.
  • sulfonating agent of the present invention a known sulfonating agent such as chlorosulfonic acid, fuming sulfuric acid, sulfur trioxide, sulfur trioxide triethyl phosphate, concentrated sulfuric acid, trimethylsilyl chlorosulfate, or the like may be used.
  • chlorosulfonic acid fuming sulfuric acid, sulfur trioxide, sulfur trioxide triethyl phosphate, concentrated sulfuric acid, trimethylsilyl chlorosulfate, or the like
  • chlorosulfonic acid fuming sulfuric acid, sulfur trioxide, sulfur trioxide triethyl phosphate, concentrated sulfuric acid, trimethylsilyl chlorosulfate, or the like.
  • chlorosulfonic acid it is more preferable to use from the viewpoint of easy introduction of sulfonic acid groups, characteristics of the obtained membrane, industrial availability, and the like.
  • the organic solvent that can be used in the present invention is not particularly limited as long as it does not deteriorate the polymer film or lose the sulfonating ability of the sulfonating agent.
  • the organic solvent used in the present invention is a halogenated hydrocarbon compound. Considering characteristics such as ringability, ease of control of introduction of sulfonic acid groups, etc., it is a halogenated hydrocarbon containing 3 or more carbon atoms and at least 1 or more chlorine atoms in the molecular structural formula.
  • the organic solvent that can be used in the present invention is not particularly limited, but is preferably a halogenated hydrocarbon compound.
  • the organic solvent is preferably an organic solvent containing 3 or more carbon atoms and at least one or more chlorine atoms in its molecular structural formula.
  • 1 Chloroprone, 1 chlorobutane, 2 chlorobutane, 1, 4 -Dichlorobutane, 1 chloro-2-methinolepronone, 1 black mouth pentane, 1 black mouth hexane, chlorocyclohexane power is also preferred, but it is preferably at least one selected. Absent.
  • 1-chlorobutane is preferred from the viewpoint of industrial availability and the characteristics of the obtained proton conductive polymer membrane.
  • the amount of the sulfonating agent used is preferably 0.1 to: LOO times (weight ratio), more preferably 0.5 to 50 times (weight ratio) with respect to the polymer film. . If the amount of the sulfonating agent used is less than 0.1 times, the amount of sulfonic acid groups introduced will be small, and the resulting polymer electrolyte membrane may have insufficient properties such as proton conductivity. There is. On the other hand, when the amount exceeds 100 times, the polymer film is chemically deteriorated, the mechanical strength of the resulting polymer electrolyte membrane is lowered, handling becomes difficult, and the introduction amount of sulfonic acid groups is large. As a result, the practical properties of the polymer electrolyte membrane may be impaired, for example, the methanol barrier property may be lowered, or it may become water-soluble or soluble in an aqueous methanol solution.
  • the amount of the sulfonating agent to be used is preferably 0.5 to 50 times, more preferably 0.5 to 30 times the weight of the polymer film.
  • the amount of sulfonating agent used If the amount is less than 0.5 times the weight of the polymer film, the amount of sulfonic acid groups introduced will be small, and the properties of the resulting proton conducting polymer membrane will be insufficient. Tend to be. On the other hand, when the amount exceeds 50 times, the polymer film is chemically deteriorated and the resulting proton conductivity is high.
  • the concentration of the sulfonating agent in the organic solvent may be appropriately set in consideration of the target introduction amount of the sulfonic acid group and the reaction conditions (temperature and time). Specifically, a more preferable range of 0.05 to 20% by weight is 0.2 to 10% by weight. If the content is lower than 0.05% by weight, the sulfonating agent and the aromatic unit in the polymer film come into contact with each other, and it is difficult to introduce the desired amount of sulfonic acid groups, or it takes time to introduce them. There is a risk of overloading. On the other hand, if it exceeds 20% by weight, the introduction of sulfonic acid groups may become uneven, and the mechanical properties of the resulting polymer electrolyte membrane may be impaired.
  • the concentration of the sulfonating agent in the solvent may be appropriately set in consideration of the target introduction amount of the sulfonic acid group and the reaction conditions (temperature 'time). Specifically, a more preferred range of 0.1 to 10% by weight is 0.2 to 10% by weight. 0. If it is lower than 1% by weight, the sulfonating agent and the aromatic unit in the polymer compound come into contact with each other, and the desired sulfonic acid group cannot be introduced, or it takes too much time to introduce it. Tend. On the other hand, if it exceeds 10% by weight, the introduction of sulfonic acid groups tends to be uneven, and the mechanical properties of the resulting proton conducting polymer membrane tend to be impaired.
  • the reaction temperature and reaction time for contacting are not particularly limited, but 0 to: L00. C, more preferably 10 to 30 ° C., 0.5 hour or more, and more preferably 2 to: L00 hours. If the reaction temperature is lower than o ° c, measures such as cooling on the equipment will be required, and the reaction may take longer than necessary. If the reaction temperature exceeds 100 ° C, the reaction will proceed excessively, There is a risk of causing side reactions and deteriorating the characteristics of the film.
  • it is less than the boiling point of the organic solvent to be used because it is not necessary to use a pressure vessel.
  • reaction time is shorter than 0.5 hour
  • the polymer electrolyte membrane having desired characteristics may be set so that it can be produced efficiently.
  • the reaction temperature and reaction time for contacting are not particularly limited, but 0 to: LOO. C, more preferably 10 to 30 ° C., 0.5 hours or more, and more preferably 2 to: LOO time.
  • LOO. C lower than o ° c
  • measures such as cooling are required on the equipment, and there is a tendency that more time is required for the reaction, and when it exceeds 100 ° C, the reaction proceeds excessively. There is a tendency to cause side reactions and to deteriorate the characteristics of the film.
  • reaction time is shorter than 0.5 hour
  • the proton conducting polymer membrane having the desired characteristics is efficiently produced in consideration of the reaction system such as the sulfonating agent and solvent used and the target production volume.
  • a polymer film composed of an aliphatic polymer compound and an aromatic polymer compound is produced by using an extruder in which a T-die is set in a twin-screw kneading extruder, and using an aliphatic polymer compound such as polyethylene or aromatic polymer. It can be obtained by melt-kneading pellets of two kinds of polymer compounds, polyphenylene sulfide as a polymer compound. When the obtained polymer film and 1-chlorobutane are used as the solvent and chlorosulfonic acid is used as the sulfonating agent, the amount of chlorosulfonic acid added is based on the weight of the polymer film.
  • the desired ion exchange capacity is achieved under the conditions that the concentration of chlorosulfonic acid in a chlorobutane solution is 0.1% by weight or more, the reaction temperature is 10 ° C or more, and the reaction time is 3 hours or more.
  • a proton conducting polymer membrane can be prepared.
  • Nyachlorosulfonic acid is removed, and sulfonic acid group-containing polyphenylene sulfide is obtained.
  • sulfonic acid groups can be introduced in the form of a film (membrane). Therefore, compared to the conventional method of synthesizing a sulfonated polymer with a homogeneous reaction system and then processing it into a membrane shape, the process of recovering and purifying the reactants, drying, etc., dissolving the sulfonated polymer in a solvent In addition, it is preferable because steps such as coating on the support and solvent removal can be omitted. Furthermore, since the film is continuously supplied, its productivity is remarkably improved.
  • the proton conductive polymer membrane can be recovered in a form that can be actually used.
  • the drying conditions may be appropriately set in consideration of the type of polymer film to be used and the characteristics of the proton conductive polymer membrane to be obtained. Since the sulfonic acid group has a strong hydrophilicity, it may contain water and swell significantly during the washing process. Therefore, it shrinks during drying and may cause wrinkles and swelling. Therefore, when drying, it is preferable to dry by applying an appropriate tension in the surface direction of the proton conducting polymer membrane. Moreover, in order to suppress rapid drying, you may dry gradually under humidity control.
  • the method for producing a polymer electrolyte membrane of the present invention may be carried out continuously. That is, a polymer film of the present invention is produced from a polymer compound prepared at a predetermined compounding ratio by melt extrusion using a twin-screw extruder with a T-die set, and the polymer film is made up of a sulfonating agent and an organic solvent. It may be supplied to the sulfonation reaction tank, and the washing process and the drying process may be continuously performed as necessary. By this method, the productivity of the polymer electrolyte membrane is improved. [0171] The method for producing a proton-conductive polymer membrane of the present invention may be carried out continuously.
  • a film made of a polymer compound to be processed is supplied to the stretching process, and further supplied to a reaction tank with a sulfonating agent, and a washing process or a drying process is performed as necessary. You may carry out continuously. This method improves the productivity of the proton conductive polymer membrane.
  • the sulfonic acid group can be introduced in the form of the film (membrane) by bringing the polymer film into contact with the sulfonating agent in the presence of the organic solvent in the sulfone reaction vessel. . Therefore, compared to the conventional method of synthesizing a polymer compound with a sulfonic acid group introduced in a homogeneous reaction system and then processing it into a membrane shape, the process of recovering and purifying the reactants, drying, and other processes, It is preferable because steps such as dissolution of a molecular compound, coating on a support during casting and removal of a solvent can be omitted. Furthermore, since the polymer film is continuously supplied, the productivity is significantly improved.
  • the conditions for removal and washing can be set appropriately in consideration of the type of sulphonating agent and organic solvent used, and the composition of the polymer film. Alternatively, neutralization may be performed using an alkali.
  • the polymer electrolyte membrane can be recovered in a practically usable form. The drying conditions may be appropriately set in consideration of the type of polymer film used and the characteristics of the polymer electrolyte membrane to be obtained.
  • the sulfonic acid group Since the sulfonic acid group has strong hydrophilicity, it may contain water and swell significantly during the washing process. For this reason, it may shrink during drying, causing wrinkles and swelling. Therefore, it is preferable to dry by applying an appropriate tension in the surface direction of the polymer electrolyte membrane during drying. Moreover, in order to suppress rapid drying, it may be gradually dried under humidity control.
  • sulfide unit (-S-) of the ido is a sulfoxide unit (so) or a sulfone unit (so
  • Oxidation or side reactions may occur where the hydrogen of the aromatic unit is replaced by a substituent such as —C1.
  • a structural unit resulting from the side reaction may be included as long as the properties of the obtained polymer electrolyte membrane are not significantly deteriorated.
  • the sulfide unit (S) in the polymer film is changed to the sulfoxide unit ( SO) to sulfone unit (SO)
  • sulfoxide unit (monoso-) is oxidized to sulfone unit (monoso2-), and hydrogen of the phenolic unit is substituted with a substituent such as C1.
  • a reaction may occur.
  • a structural unit resulting from the side reaction may be included.
  • FIG. 1 is a cross-sectional view of the main part of a solid polymer fuel cell (direct liquid fuel cell, direct methanol fuel cell) using the polymer electrolyte membrane of the present invention.
  • a polymer electrolyte membrane 1, a catalyst layer 2 in contact with the polymer electrolyte membrane 1, a catalyst layer 2, a diffusion layer 3 in contact with the polymer electrolyte membrane 1, and a separator 5 on the outer side thereof are disposed, and a solid polymer type It consists of fuel cell (direct liquid fuel cell, direct methanol fuel cell) cells. Separator 5 is formed with fuel gas or liquid (such as aqueous methanol solution) and 5 for feeding an oxidant.
  • a polymer electrolyte membrane 1 joined with a catalyst layer 2 or a polymer electrolyte membrane 1 joined with a catalyst layer 2 and a diffusion layer 3 is a membrane-electrode assembly (hereinafter referred to as a membrane-electrode assembly).
  • a membrane-electrode assembly Is called the base of solid polymer fuel cells (direct liquid fuel cells, direct methanol fuel cells). Used as this member.
  • the catalyst layer 2 is formed by dispersing a metal-supported catalyst in a polymer electrolyte solution or dispersion to prepare a dispersion for forming the catalyst layer.
  • This dispersion solution is applied onto a release film such as polytetrafluoroethylene by spraying, and the solvent in the dispersion solution is dried and removed to form a predetermined catalyst layer 2 on the release film.
  • the catalyst layer 2 formed on the release film is disposed on both surfaces of the polymer electrolyte membrane 1, and hot-pressed under a predetermined heating and pressurizing condition to join the polymer electrolyte membrane 1 and the catalyst layer 2, By peeling off the release film, an MEA in which the catalyst layer 2 is formed on both surfaces of the polymer electrolyte membrane 1 can be produced. Further, the dispersion solution is applied onto the diffusion layer 3 using a coater or the like, and the solvent in the dispersion solution is dried and removed to form a catalyst-carrying gas diffusion electrode in which the catalyst layer 2 is formed on the diffusion layer 3.
  • both sides of the polymer electrolyte membrane 1 are prepared.
  • An MEA having a catalyst layer 2 and a diffusion layer 3 formed thereon can be produced.
  • a commercially available gas diffusion electrode manufactured by E-TEK, USA, etc. may be used.
  • an alcohol solution of a perfluorocarbon sulfonic acid polymer compound such as a naphthion (registered trademark) solution manufactured by Aldrich
  • a sulfonated aromatic polymer compound for example, Sulfonized polyetheretherketone, sulfonated polyethersulfone, sulfonated polysulfone, sulfonated polyimide, sulfonated polyphenylene sulfide
  • a perfluorocarbon sulfonic acid polymer compound such as a naphthion (registered trademark) solution manufactured by Aldrich
  • a sulfonated aromatic polymer compound for example, Sulfonized polyetheretherketone, sulfonated polyethersulfone, sulfonated polysulfone, sulfonated polyimide, sulfonated polyphenylene sulfide
  • metal-supported catalyst conductive particles having a high specific surface area can be used as
  • activated carbon, carbon black, ketjen black, vulcan, carbon nanohorn examples thereof include carbon materials such as allene and carbon nanotubes.
  • Any metal catalyst can be used as long as it promotes the acid-rich reaction of the fuel and the oxygen reduction reaction, and the fuel electrode and the oxidant electrode may be the same or different.
  • noble metals such as platinum and ruthenium or alloys thereof can be exemplified, and a promoter for promoting their catalytic activity and suppressing poisoning by reaction by-products may be added.
  • the dispersion solution for forming the catalyst layer may be appropriately diluted with water or an organic solvent in order to adjust the viscosity so that it can be applied with a spray or easily applied with a coater.
  • a fluorine compound such as tetrafluoroethylene may be mixed to impart water repellency to the catalyst layer 2.
  • a porous conductive material such as carbon cloth or carbon paper can be used.
  • an adhesive layer containing the polymer electrolyte as described above may be provided between the polymer electrolyte membrane 1 and the catalyst layer 2 as necessary.
  • the conditions under which the polymer electrolyte membrane 1 and the catalyst layer 2 are heated and hot pressed under pressure are appropriately set according to the type of polymer electrolyte contained in the polymer electrolyte membrane 1 and the catalyst layer 2 to be used. There is a need.
  • the temperature is lower than the thermal deterioration or thermal decomposition temperature of the polymer electrolyte membrane or the polymer electrolyte, and the temperature of the polymer electrolyte membrane 1 is higher than the glass transition point or the soft melting point of the polymer electrolyte. Is preferably carried out under temperature conditions above the glass transition point and softening point of the polymer electrolyte membrane 1 and the polymer electrolyte.
  • the pressurizing condition is preferably in the range of about 0.1 MPa to 20 MPa because there is sufficient contact between the polymer electrolyte membrane 1 and the catalyst layer 2 and there is no deterioration in characteristics due to significant deformation of the materials used.
  • the diffusion layer 3 may be disposed outside the catalyst layer 2 and used only by contacting them without any particular bonding. .
  • the MEA obtained by the method as described above is inserted between a pair of separators 4 in which a flow path 5 for feeding fuel gas or liquid and an oxidant is formed.
  • a polymer electrolyte fuel cell (direct liquid fuel cell, direct methanol fuel cell) containing an electrolyte membrane can be obtained.
  • a fuel gas or liquid a gas mainly composed of hydrogen or a gas or liquid mainly composed of methanol is used as an oxidizing agent.
  • the polymer electrolyte fuel cell generates electric power by supplying gas (oxygen or air) containing element to the catalyst layer 2 via the diffusion layer 3 from the respective separate flow paths 5.
  • gas oxygen or air
  • a force bone graphite or a stainless steel conductive material can be used. Especially when using metal materials such as stainless steel, it is preferable to apply a corrosion-resistant treatment!
  • the polymer electrolyte fuel cells of the present invention may be used alone or in a stack to form a stack, and a fuel cell system incorporating them may be used.
  • FIG. 13 is a cross-sectional view of a main part of a solid polymer fuel cell (direct liquid fuel cell, direct methanol fuel cell) using the proton conductive polymer membrane of the present invention.
  • a method of joining the catalyst-carrying gas diffusion electrode 22 to the proton conductive polymer membrane 21 has been studied, and a proton conductive polymer membrane made of a perfluorocarbon sulfonic acid membrane, Proton conducting polymer membranes made of polymer compounds
  • an alcohol solution of a perfluorocarbon sulfonic acid polymer such as a naphthion (registered trademark) solution manufactured by Aldrich
  • a sulfonated polymer constituting the proton conductive polymer membrane of the present invention Compound or known sulfonated polymer compound
  • the proton conductive polymer membrane of the present invention using, as a binder, an organic solvent solution (for example, sulfonated polyetheretherketone, sulfonated polyethersulfone, sulfonated polysulfone, sulfonated polyimide, sulfonated polyphenylene sulfide).
  • the surface on the catalyst layer side of the catalyst-carrying gas diffusion electrode 22 is aligned with both surfaces of 21, and using a press such as a hot press or a portal press, the press temperature is typically about 120 to 250 ° C. Can be joined. Moreover, it is not necessary to use a binder as needed. Furthermore, the catalyst-supporting gas diffusion electrode 22 may be prepared using the following materials and bonded to the proton conducting polymer membrane 21 for use.
  • the material used to prepare the catalyst-carrying gas diffusion electrode 22 is a metal such as platinum or ruthenium or an alloy thereof that promotes the oxidation reaction of fuel and the reduction reaction of oxygen as a catalyst.
  • carbon cloth, carbon paper, etc. as a support for the above materials, and perfluorocarbon sulfonic acid polymer as an impregnated coating material can be exemplified.
  • the present invention is not limited to this. is not.
  • the proton-conductive polymer membrane 21 obtained by the method as described above and the catalyst-supported gas diffusion electrode 22 are joined to form a flow path 23 for feeding fuel gas or liquid and an oxidant.
  • the polymer electrolyte fuel cell comprising the proton conducting polymer membrane of the present invention (direct liquid fuel cell, direct methanol fuel) Battery).
  • a gas containing hydrogen as a main component, a gas or liquid mainly containing methanol as a fuel gas or liquid, and a gas containing oxygen (oxygen or air) as an oxidizing agent are provided in separate flow paths.
  • the solid polymer fuel cell is operated by supplying the catalyst-carrying gas diffusion electrode 22 from 23. In this case, when methanol is used as the fuel, a direct methanol fuel cell is obtained.
  • Fig. 2 is a cross-sectional view of a principal part of a direct methanol fuel cell including the polymer electrolyte membrane of the present invention.
  • the required number of MEAs 6 obtained by the above method is arranged in a plane on both sides of a fuel (methanol or methanol aqueous solution) tank 7 having a fuel (methanol or methanol aqueous solution) filling section 8 and a supply section 8. Further, a support 9 having an oxidant flow path 10 formed thereon is disposed on the outer side, and these cells are sandwiched to form a direct methanol fuel cell cell and stack.
  • Fig. 14 is a cross-sectional view of a main part of a direct methanol fuel cell comprising the proton conductive polymer membrane of the present invention.
  • the proton conducting polymer membrane 25 and the catalyst-supporting electrode 26 are joined to both sides of the membrane 25 to form a membrane-electrode assembly.
  • This membrane-electrode assembly is arranged in a planar form on both sides of a fuel (methanol or methanol aqueous solution) tank 27 having a fuel (methanol or methanol aqueous solution) filling section 28 and a supply section 28.
  • a support 29 having an oxidant flow path 30 formed thereon is disposed on the outside thereof, and these cells are sandwiched to form a direct methanol fuel cell cell and stack.
  • the polymer electrolyte membrane of the present invention is disclosed in JP 2001-313046, JP 2001-313047, JP 2001-93551, and JP 2001-93558.
  • the proton conductive polymer membrane of the present invention is disclosed in JP-A-2001-313046, JP-A-2001-313047, JP-A-2001-93551, and JP-A-2001-93.
  • JP 2001-283888 JP 2000-268835, JP 2000-268836, JP 2001-283892, etc. It can be used as an electrolyte membrane of a direct methanol fuel cell.
  • the aliphatic polymer compound X XYIII used in the proton-conductive polymer electrolyte of the present invention and the polymer film of the material thereof refers to a compound that does not have an aromatic unit in its structural unit. In the case of a conductive polymer electrolyte membrane, it constitutes a structural unit that does not contain a proton conductive substituent. Examples of such aliphatic polymer compounds include the following formulas (4) to (6):
  • X and Y are H, CH, Cl, F, OCOCH, CN, COOH, COOCH, OC H, or
  • any of atomic groups selected from 3 3 3 4 9, and X and Y may be the same or different from each other.
  • at least one selected from the aliphatic polymer compounds having a repeating unit represented by the formula is excellent in chemical and thermal stability and processability, it is also inexpensive. Favorable because it is industrially available.
  • X in the formula (4) is H, CH, Cl, F, and X and Y in the formula (5) are (X,
  • X in (F, F) and formula (6) is at least one selected from an aliphatic polymer compound comprising a repeating unit represented by F or H as a chemical or thermal compound. It is preferable because it is excellent in stability and processability, and is industrially available at a low cost.
  • the aromatic polymer compound in the present invention is a high molecular compound having an aromatic ring in the main chain or side chain, and is not particularly limited.
  • Examples of the aromatic polymer compound containing a proton conductive group of the present invention include polyaryl ether sulfone, polyether ether sulfone, polyether ether ketone, polyether ketone ketone, polysulfone, and polyparaphenylene.
  • the polymer is at least one of polyethylene-polysulfide, polyphenylene ether, polystyrene, syndiotactic polystyrene, polyethersulfone, and polyetheretherketone.
  • the content of the aliphatic polymer compound in the proton conductive polymer electrolyte is preferably 10 wt% or more and 95 wt% or less. If the aliphatic polymer compound content is smaller than the above range, There is a possibility that the inclusion effect of the group-based polymer compound becomes unclear. On the other hand, when the content of the aliphatic polymer compound is larger than the above range, proton conductivity may be difficult to express.
  • a high proton conductivity is obtained by contacting a polymer film having at least two kinds of polymer compounds of the aliphatic polymer compound of the present invention and an aromatic polymer compound with a sulfonating agent.
  • a method for producing a molecular electrolyte membrane and a method for producing a polymer film as the material will be described.
  • At least two kinds of high molecular compounds that is, an aliphatic high molecular compound and an aromatic high molecular compound
  • a known method can be applied.
  • the casting method it may be mixed in a solution. Further, it may be uniformly dispersed by melt kneading. In this case, melt kneading may be performed twice in order to increase dispersibility.
  • melt kneading may be performed twice in order to increase dispersibility.
  • melt kneading may be performed twice in order to increase dispersibility.
  • melt kneading may be performed twice in order to increase dispersibility.
  • melt kneading may be performed twice in order to increase dispersibility.
  • melt kneading may be performed twice in order to increase dispersibility.
  • the thickness of the polymer film consisting of an aliphatic polymer compound and an aromatic polymer compound having at least two kinds of polymer compounds can be any thickness depending on the application. Can be selected. In consideration of reducing the internal resistance of the obtained polymer electrolyte membrane, the thinner the polymer film, the better. On the other hand, considering the methanol blocking properties of the obtained polymer electrolyte membrane, the polymer film thickness is not preferable if it is too thin. Considering these, the thickness of the polymer film is 1.! It is preferably ⁇ 350 / z m.
  • the thickness of the polymer film is thinner than 1., it is difficult to produce, and it tends to become wrinkled during processing, and the handling property tends to be difficult due to breakage. If the thickness of the polymer film exceeds 350 m, the resulting polymer electrolyte membrane may not exhibit the effect of improving the methanol barrier property.
  • the issues are "solid polymer fuel cell, direct liquid fuel cell, direct methanol fuel A polymer electrolyte membrane having excellent proton conductivity and high methanol-blocking properties useful as a constituent material of a battery and a method for producing the same, and a polymer film as a material for the polymer electrolyte membrane and the polymer film A manufacturing method is provided. That ’s it.
  • a polymer electrolyte membrane useful as a constituent material of a solid polymer fuel cell, a direct liquid fuel cell, a direct methanol fuel cell, a polymer film that is a material thereof, and production of the electrolyte membrane The present invention provides a polymer electrolyte fuel cell using a method and an electrolyte membrane.
  • the means for solving the problem is that "a high-molecular compound containing at least three kinds of polymer compounds having an aromatic unit, a thermoplastic elastomer, and a polymer compound having no aromatic unit as essential components. It is assumed that the proton conductive group is introduced into the aromatic unit in the molecular film. "
  • the solving means is that "the polymer compound having at least two kinds of polymer compounds, that is, the polymer compound having an aromatic unit and the polymer compound having no aromatic unit, and having no said aromatic unit".
  • the polymer compound having an aromatic unit is dispersed therein, and a proton conductive group is introduced into the aromatic unit in the polymer film having the above structure.
  • the solving means is "a polymer electrolyte membrane having at least two kinds of polymer compound power of an aliphatic polymer compound and an aromatic polymer compound containing a proton conductive group.
  • the electrolyte membrane has a structure in which a proton conductive group is bonded to an aromatic polymer compound present in a polymer film as a material.
  • Polyphenylene sulfide manufactured by Dainippon Ink & Chemicals, LDlOplll
  • high density as a polymer compound having no aromatic unit
  • Polyethylene manufactured by Mitsui Engineering Co., Ltd., HI-ZEX 3300F
  • a polymer electrolyte membrane (about 10 mm ⁇ 40 mm) was immersed in 20 mL of a saturated aqueous solution of sodium chloride at 25 ° C., and subjected to an ion exchange reaction at 60 ° C. for 3 hours in a water bath. After cooling to 25 ° C, the membrane was thoroughly washed with ion-exchanged water, and all the sodium chloride saturated aqueous solution and washing water were collected. To this recovered solution, a phenolphthalein solution was added as an indicator, and neutralization titration with 0.01N sodium hydroxide aqueous solution was performed to calculate the ion exchange capacity.
  • 2-pole non-sealed polytetrafluoroethylene A polymer electrolyte membrane was placed in a cell made of copper, and a platinum electrode was placed on the membrane surface (on the same side) so that the distance between the electrodes was 30 mm.
  • Membrane resistance at 23 ° C was measured by an AC impedance method (frequency: 42 Hz to 5 MHz, applied voltage: 0.2 V, Hioki LCR meter 3531Z HIT ESTER), and proton conductivity was calculated.
  • ion exchange water and a 64 wt% aqueous methanol solution were isolated with a polymer electrolyte membrane using a membrane permeation experiment apparatus (KH-5PS) manufactured by Beadrex. After a predetermined time (2 hours), a solution containing methanol that had permeated to the ion-exchanged water was collected, and the amount of methanol permeated was measured with a gas chromatograph (Shimadzu Gas Chromatography GC -2010). From this quantitative result, the methanol permeation rate was determined, and the methanol permeation coefficient was calculated.
  • the methanol permeability coefficient was calculated according to Equation 1 below.
  • a polymer film of the present invention was obtained in the same manner as in Example 1 except that 50 parts by weight of pellets of polyphenylene sulfide and 50 parts by weight of high density polyethylene pellets were used (high density polyethylene in the polymer film). 50% by weight). Further, the dispersion state of the polymer compound was observed in the same manner as in Example 1. The results are shown in Fig. 4.
  • the polymer film obtained by the above method was used.
  • a polymer electrolyte was prepared in the same manner as in Example 1 except that 141 g of 1-chlorobutane and 4.2 g of chlorosulfonic acid were weighed to prepare a 3% by weight chlorosulfonic acid solution and the polymer film was adjusted to 0.33 g.
  • a membrane was obtained (the amount of chlorosulfonic acid added was 13 times that of the polymer film). The results are shown in Table 1.
  • a polymer film of the present invention was obtained in the same manner as in Example 1 except that 30 parts by weight of polyphenylene sulfide pellets and 70 parts by weight of high density polyethylene pellets were used (high density polyethylene in the polymer film). 70% by weight). Further, the dispersion state of the polymer compound was observed in the same manner as in Example 1. The results are shown in FIG.
  • the polymer film obtained by the above method was used.
  • a polymer electrolyte was prepared in the same manner as in Example 1, except that 145 g of 1-chlorobutane and 5.8 g of chlorosulfonic acid were weighed to prepare a 4 wt% chlorosulfonic acid solution and the polymer film was adjusted to 0.33 g.
  • a membrane was obtained (the amount of chlorosulfonic acid added was 17 times that of the polymer film). The results are shown in Table 1.
  • a polymer film of the present invention was obtained in the same manner as in Example 3 except that polyphenylene sulfide (manufactured by Dainippon Ink & Chemicals, Inc., ML320p) was used as the polymer compound having an aromatic unit. (The polymer film contains 70% by weight of high-density polyethylene). Further, the dispersion state of the polymer compound was observed in the same manner as in Example 1. The result is shown in FIG.
  • the polymer film obtained by the above method was used.
  • Og was weighed to prepare a 5 wt% chlorosulfonic acid solution, and the polymer film was changed to 0.28 g.
  • a membrane was obtained (the amount of chlorosulfonic acid added was 22 times that of the polymer film). The results are shown in Table 1.
  • a polymer film of the present invention was obtained in the same manner as in Example 3 except that polypropylene (Mitsui Chemicals, Mitsui Polypro F107DV) was used as the polymer compound having no aromatic unit (high The molecular film contains 70% by weight of polypropylene). Further, the dispersion state of the polymer compound was observed in the same manner as in Example 1. The results are shown in FIG.
  • the polymer film obtained by the above method was used.
  • a polymer electrolyte was prepared in the same manner as in Example 1 except that 136 g of 1-chlorobutane and 5.4 g of chlorosulfonic acid were weighed to prepare a 4 wt% chlorosulfonic acid solution and the polymer film was adjusted to 0.31 g.
  • a membrane was obtained (the amount of chlorosulfonic acid added was 17 times that of the polymer film). The results are shown in Table 1.
  • a polymer film of the present invention was obtained in the same manner as in Example 5 except that polyphenylene sulfide (ML320p, manufactured by Dainippon Ink & Chemicals, Inc.) was used as the polymer compound having an aromatic unit. (The polymer film contains 70% by weight of polypropylene). Further, the dispersion state of the polymer compound was observed in the same manner as in Example 1. The results are shown in Fig. 8.
  • the polymer film obtained by the above method was used.
  • Og was weighed to prepare a 5 wt% chlorosulfonic acid solution, and the polymer film was changed to 0.28 g.
  • a membrane was obtained (chlorosulfo (The amount of acid added is 22 times the amount of polymer film). The results are shown in Table 1.
  • Polystyrene PS Japan Polystyrene G8102
  • a polymer compound with aromatic units a polymer compound with aromatic units
  • high-density polyethylene HI-ZEX 3300F, Mitsui Chemicals
  • the polymer film obtained by the above method was used.
  • a polymer electrolyte was prepared in the same manner as in Example 1 except that 128 g of 1-chlorobutane and 3.9 g of chlorosulfonic acid were weighed to prepare a 3% by weight chlorosulfonic acid solution and the polymer film was changed to 0.30 g.
  • a membrane was obtained (the amount of chlorosulfonic acid added was 13 times that of the polymer film). The results are shown in Table 1.
  • Polystyrene PS Japan Co., Ltd., PSJ Polystyrene G8102 was used as the polymer compound having aromatic units, and Polypropylene (Mitsui Polytechnics Corp., Mitsui Polypro F107DV) was used as the polymer compound having no aromatic units. .
  • the polymer film obtained by the above method was used.
  • a polymer electrolyte was prepared in the same manner as in Example 1 except that 91 g of 1-chlorobutane and 4.6 g of chlorosulfonic acid were weighed to prepare a 5 wt% chlorosulfonic acid solution and the polymer film was changed to 0.21 g.
  • a membrane was obtained (the amount of chlorosulfonic acid added was 22 times that of the polymer film). The results are shown in Table 1.
  • Modified polyphenylene ether (GE Japan, EFN4230) was used as the polymer compound having an aromatic unit, and high-density polyethylene (HI-ZEX 3300F, manufactured by Mitsui Chemicals, Inc.) was used as the polymer compound having no aromatic unit.
  • the polymer film obtained by the above method was used. Except for weighing 91 g of 1-chlorobutane and 1.4 g of chlorosulfonic acid, preparing a 1.5 wt% chlorosulfonic acid solution and changing the polymer film to 0.21 g, the same procedure as in Example 1 was followed. A molecular electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 6.7 times that of the polymer film). The results are shown in Table 1.
  • a polymer film of the present invention was obtained in the same manner as in Example 9 except that polypropylene (Mitsui Chemicals, Mitsui Polypro F107DV) was used as the polymer compound having no aromatic unit. Contains 70% by weight polypropylene). Further, the dispersion state of the polymer compound was observed in the same manner as in Example 1. The results are shown in FIG.
  • Polyphenylene sulfide (manufactured by Dainippon Ink & Chemicals, Inc., DIC-PPS LDlOpl) was used as a polymer compound having an aromatic unit.
  • the polyphenylene sulfide pellets were melt-extruded using a twin-screw extruder in which a T-die was set in a twin-screw kneading extruder under the conditions of a screw temperature of 290 ° C and a T-die temperature of 290 ° C. A polymer film was obtained.
  • the polymer film obtained by the above method was used.
  • lg was weighed to prepare a 1.5% by weight chlorosulfonic acid solution, and the polymer film was adjusted to 0.16 g.
  • a polymer electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 6.9 times that of the polymer film). The results are shown in Table 1.
  • Nafion (registered trademark) 115 manufactured by DuPont was used as the polymer electrolyte membrane. The results are shown in Table 1.
  • the polymer film of the present invention has an aromatic in the polymer compound (whitish portion) having no aromatic unit. It became clear that the polymer compound with the unit (black part) showed a dispersed structure.
  • Examples 1 to in Table 1 From the comparison between LO and Comparative Example 2, the polymer electrolyte membrane obtained according to the present invention was a polymer electrolyte membrane for a polymer electrolyte fuel cell. It became clear that it has proton conductivity of the same order as that of a certain comparative example 2, and was shown to be useful as a polymer electrolyte membrane of a solid polymer fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell. . [0259] Examples 1 to in Table 1: From the comparison between LO and Comparative Examples 1 and 2, the polymer electrolyte membrane obtained with the polymer film strength of the present invention has a conventional high conductivity that exhibits equivalent proton conductivity.
  • Example 1 From a comparison between Example 1 and Tables 2 and 3 in Table 1, it is clear that the content of the polymer compound having no aromatic unit is 40% by weight or more, indicating a higher methanol barrier property. Thus, the usefulness of the present invention was demonstrated.
  • Polystyrene PS Japan Co., Ltd., PSJ Polystyrene G8102
  • Polystyrene polyethylene Z-butylene
  • Polystyrene triblock copolymer (Septon 8104, manufactured by Kuraray Co., Ltd.) as a thermoplastic elastomer
  • High-density polyethylene manufactured by Mitsui Chemicals, Inc., HI-ZEX 3300F was used as a polymer compound having no aromatic unit.
  • a polymer electrolyte membrane (about 10 mm ⁇ 40 mm) was immersed in 20 mL of a saturated aqueous solution of sodium chloride at 25 ° C., and subjected to an ion exchange reaction at 60 ° C. for 3 hours in a water bath. After cooling to 25 ° C, the membrane was thoroughly washed with ion-exchanged water, and all the sodium chloride saturated aqueous solution and washing water were collected. To this recovered solution, a phenolphthalein solution was added as an indicator, and neutralization titration with 0.01N sodium hydroxide aqueous solution was performed to calculate the ion exchange capacity.
  • a polyelectrolyte membrane was placed in a cell made of polytetrafluoroethylene in a nonpolar hermetic system, and a platinum electrode was placed on the membrane surface (on the same side) so that the distance between the electrodes was 30 mm.
  • the membrane resistance at 23 ° C was measured by the AC impedance method (frequency: 42 Hz to 5 MHz, applied voltage: 0.2 V, Hioki LCR meter 3531Z HIT ESTER), and proton conductivity was calculated.
  • ion exchange water and a 64 wt% aqueous methanol solution were isolated with a polymer electrolyte membrane using a membrane permeation experiment apparatus (KH-5PS) manufactured by Beadrex. After a predetermined time (2 hours), a solution containing methanol permeated to the ion-exchanged water was collected, and the amount of methanol permeated was quantified with a gas chromatograph (Shimadzu Gas Chromatography GC-2010). From this quantitative result, the methanol permeation rate was determined, and the methanol permeation coefficient was calculated.
  • the methanol permeability coefficient was calculated according to Equation 1 below.
  • the present invention was carried out in the same manner as in Example 11, except that 20 parts by weight of polystyrene pellets, 5 parts by weight of polystyrene poly (ethylene Z-butylene) polystyrene triblock copolymer pellets, and 80 parts by weight of high-density polyethylene pellets were used.
  • Polymer film contains 76% by weight of high-density polyethylene.
  • the polymer film obtained by the above method was used.
  • 1-Chlorobutane 84.7 g and chlorosulfonic acid 0.21 g were weighed to prepare a 0.25 wt% chlorosulfonic acid solution, and the polymer film was changed to 0.20 g.
  • the polymer electrolyte membrane was obtained by this method (the amount of chlorosulfonic acid added was 1.1 times that of the polymer film). The results are shown in Table 2.
  • a polymer film of the present invention was obtained in the same manner as in Example 12 (76% by weight of high-density polyethylene was contained in the polymer film).
  • Polystyrene PS Japan Co., Ltd., PSJ Polystyrene G8102 as a polymer compound having an aromatic unit
  • Polystyrene poly (ethylene Z propylene) -polystyrene triblock copolymer as a thermoplastic elastomer (Kuraray Co., Ltd., Septon 2104)
  • Polypropylene Mitsubishi Chemicals, Mitsui Polypro F107DV was used as a high molecular compound having no aromatic unit.
  • polystyrene pellets 5 parts by weight of polystyrene poly (ethylene Z propylene) polystyrene triblock copolymer pellets, and 70 parts by weight of high density polyethylene pellets were dry blended.
  • the dry blended pellet mixture was melt-extruded by a twin screw extruder with a T die set under the conditions of a screw temperature of 265 ° C and a T die temperature of 265 ° C to obtain the polymer film of the present invention (high polypropylene 67 weight 0/0 contained in the molecule film).
  • the polymer film obtained by the above method was used. 1 Weigh 93.0 g of chlorobutane and 0.12 g of chlorosulfonic acid to prepare a 0.13% by weight chlorosulfonic acid solution and change the polymer film to 0.22 g. A polymer electrolyte membrane was obtained (the amount of black sulfonic acid added was 0.5 times that of the polymer film). The results are shown in Table 2.
  • the polymer film obtained by the above method was used. Except that 101-lg of 1-chlorobutane and 0.51 g of chlorosulfonic acid were weighed to prepare a chlorosulfonic acid solution of 0.50% by weight and the polymer film was changed to 0.23 g, the same as in Example 11. Thus, a polymer electrolyte membrane was obtained (the amount of blackened sulfonic acid added was 2.2 times that of the polymer film). The results are shown in Table 2.
  • polystyrene-poly (ethylene Z-butylene) -polystyrene triblock copolymer Kuraray Co., Ltd., Septon 8104
  • polystyrene-poly (ethylene Z propylene) -polystyrene triblock copolymer ethylene Z propylene
  • the polymer film obtained by the above method was used. 1 Weigh 70.lg of chlorobutane and 0.18 g of chlorosulfonic acid, prepare a 0.25 wt% chlorosulfonic acid solution, and adjust the polymer film to 0.16 g. A polymer electrolyte membrane was obtained (the amount of black sulfonic acid added was 1.1 times that of the polymer film). The results are shown in Table 2.
  • Polyphenylene sulfide manufactured by Dainippon Ink & Chemicals, Inc., DIC-PPS LDlOpl l l was used as a polymer compound having an aromatic unit.
  • the polyphenylene sulfide pellets were melt-extruded by a twin-screw extruder in which a T-die was set in a twin-screw kneading extruder under the conditions of a screw temperature of 290 ° C and a T-die temperature of 290 ° C. A polymer film was obtained.
  • Nafion (registered trademark) 115 manufactured by DuPont was used as the polymer electrolyte membrane. The results are shown in Table 2.
  • the polymer electrolyte membrane obtained according to the present invention was a polymer electrolyte membrane for a polymer electrolyte fuel cell. It was revealed that the proton conductivity was of the same order as in Comparative Example 3, and it was shown that the polymer was useful as a polymer electrolyte membrane for a solid polymer fuel cell, a direct liquid fuel cell, and a direct methanol fuel cell.
  • the polymer electrolyte membrane from which the polymer film force of the present invention was obtained is a conventional polymer exhibiting equivalent proton conductivity. Compared with electrolyte membranes, it has a low methanol permeability coefficient and a high methanol barrier property, and is useful as a polymer electrolyte membrane for direct liquid fuel cells such as direct methanol fuel cells. It has been shown.
  • high-density polyethylene manufactured by Mitsui Engineering Co., Ltd., HI-Z EX 3300F
  • Polyphenylene sulfide manufactured by Dainippon Ink Industries, Ltd., DIC-PPS LDlOpl l
  • aromatic polymer compound was used as the aromatic polymer compound.
  • the ion exchange capacity of the polymer electrolyte membrane was measured by the following method.
  • a polymer electrolyte membrane of about 10 mm ⁇ 40 mm was immersed in 20 mL of a saturated sodium chloride aqueous solution at 25 ° C. and reacted at 60 ° C. for 3 hours in a water bath. After cooling to 25 ° C, the membrane was thoroughly washed with ion-exchanged water, and all sodium chloride saturated aqueous solution and washing water were collected. To this collected solution, a phenolphthalein solution was added as an indicator, and neutralization titration with 0.01N aqueous sodium hydroxide was performed to calculate the ion exchange capacity. The results are shown in Table 3.
  • the proton conductivity of the polymer electrolyte membrane was measured by the following method.
  • Proton conductivity The polymer electrolyte membrane was cut into a circular shape with a diameter of 16 mm, and excess moisture was wiped off with filter paper before being used for measurement.
  • Stainless steel electrodes are attached to both front and back sides of the test specimen, and these are placed in a bipolar metal cell. Then, the AC impedance method (frequency: 42Hz, 5MHz) LCR meter 3531Z HITESTER) was used to measure membrane resistance and calculate film thickness proton conductivity. The results are shown in Table 3. [0294] Further, the methanol blocking property of the polymer electrolyte membrane was measured by the following method.
  • a membrane permeation experiment apparatus manufactured by Beadrex was used.
  • Proton-conducting Polymer electrolyte membrane separates ion-exchanged water and methanol solution of a predetermined concentration, and after a predetermined time (2 hours) has elapsed, a solution containing methanol that has permeated the ion-exchanged water is collected.
  • the amount of methanol permeated by gas chromatography GC-2010 was quantified. From this quantitative result, the methanol permeation rate was determined, and the methanol permeation coefficient and methanol permeation coefficient were calculated.
  • the methanol permeability coefficient and the methanol cutoff coefficient were calculated according to the following formulas 1 and 2. The results are shown in Table 3.
  • Example 17 A polymer film obtained in the same manner as in Example 17 was used. 1-Chlorobutane 15 Og, 4.5 g of chlorosulfonic acid were weighed, 3. Proton conductivity high as in Example 17 except that an Owt% chlorosulfonic acid solution was prepared and the high molecular weight film was 0.35 g. A molecular electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 12.9 times the weight of the polymer film). The results are shown in Table 3.
  • Example 17 A polymer film obtained in the same manner as in Example 17 was used. 1-Chlorobutane 12 7g and chlorosulfonic acid 4.4g were weighed to prepare a 3.5wt% chlorosulfonic acid solution, and the high molecular film was changed to 0.29g. An electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 15.1 times the weight of the polymer film). The results are shown in Table 3.
  • Example 20 A polymer film obtained in the same manner as in Example 17 was used. 1-Chlorobutane 14 5 g and chlorosulfonic acid 5.8 g were weighed, 4. Proton conduction was conducted in the same manner as in Example 17 except that an Owt% chlorosulfonic acid solution was prepared and the high molecular weight film was changed to 0.33 g. A polymer electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 17.3 times the weight of the polymer film). The results are shown in Table 3.
  • Example 17 A polymer film obtained in the same manner as in Example 17 was used. 1-Chlorobutane 13 8 g and chlorosulfonic acid 6.2 g were weighed, a 4.5 wt% chlorosulfonic acid solution was prepared, and proton conduction was performed in the same manner as in Example 17 except that the high molecular weight film was 0.32 g. A polymer electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 19.4 times the weight of the polymer film). The results are shown in Table 3.
  • Example 17 A polymer film obtained in the same manner as in Example 17 was used. 1-Chlorobutane 12 9 g, chlorosulfonic acid 6.5 g were weighed, 5. Owt% chlorosulfonic acid solution was prepared, and proton conduction was performed in the same manner as in Example 17 except that the high molecular weight film was changed to 0.30 g. A conductive polymer electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 21.6 times the weight of the polymer film). The results are shown in Table 3.
  • Example 17 A polymer film obtained in the same manner as in Example 17 was used. Dichloromethane was used in place of 1-chlorobutane. A polymer electrolyte membrane was prepared in the same manner as in Example 17 except that 798 g of dichloromethane and 8.Og of chlorosenophonic acid were weighed, 1. Owt% chlorosulfonic acid solution was prepared, and the polymer film was changed to 1.8 g. Obtained. The results are shown in Table 3.
  • a force sword catalyst 50% platinum-supported carbon (SA50BK manufactured by Ny Chemcat) was used. A 5% naphthion (registered trademark) dispersion (manufactured by Aldrich) was used as a binder. A force sword catalyst and pure water were mixed at a weight ratio of 1:10 to obtain a solution A. The solution A and the binder were mixed with the force sword catalyst so that the binder had a weight ratio of 1: 7.3 to obtain a solution B. Platinum 27% ruthenium 13% supported carbon as anode catalyst Mcat SA27-13RCBK) was used. An anode catalyst and pure water were mixed at a weight ratio of 1:10 to obtain a solution C.
  • the solution C and the binder were mixed with the anode catalyst so that the binder had a weight ratio of 1: 7.1 to obtain a solution D.
  • the process of applying the solution B onto a 22 mm square, 50 ⁇ m thick Teflon (registered trademark) sheet washed with acetone and drying was repeated several times to obtain a platinum amount of lmg / cm 2 to obtain a force sword catalyst sheet.
  • solution D was applied to a platinum amount of lmg / cm 2 to obtain an anode catalyst sheet.
  • the polymer electrolyte membrane described in Example 23 is used, and is sandwiched between the anode catalyst sheet and the force sword catalyst sheet, and is further sandwiched in the order of 50 m thick Teflon (registered trademark) sheet, filter paper, and SUS plate. did. This was hot pressed at 150 ° C and 50 kgfZcm 2 and held for 5 minutes. After pressing, the Teflon (registered trademark) sheet, the filter paper, and the SUS plate were removed, and the Teflon (registered trademark) sheet of the catalyst sheet was removed to obtain a membrane-electrode assembly.
  • Teflon (registered trademark) dispersion (Daikin Industries POLYFLON PTFE D-1E) is applied and baked at 360 ° C for 1 hour for water repellent treatment.
  • a diffusion layer subjected to was obtained.
  • a 180 m thick, 80-square Teflon (registered trademark) sheet was cut into a 25-corner center and used as a gasket.
  • the MEA was sandwiched between a diffusion layer and a gasket and attached to a fuel cell (ElectroChem FC05-01 SP) with an electrode area of 5 cm 2 .
  • the torque pressure holding the cell at this time gradually increased from 1N'm to 2N'm, 3N'm, and 4N'm.
  • a GFT-MW manufactured by Toyo Corporation was used as the evaluation device. 1M methanol aqueous solution was supplied to the anode electrode side at a flow rate of 0.5 mLZmin, and air was supplied as an oxidizing agent to the force sword electrode side at a flow rate of 160 mLZmin. The power generation characteristics of a direct methanol fuel cell were evaluated at a cell temperature of 60 ° C. The results are shown in FIG.
  • aliphatic polymer compound high-density polyethylene (manufactured by Mitsui Engineering Co., Ltd., HI-Z EX 3300F) was used.
  • Polyphenylene sulfide manufactured by Dainippon Ink Industries, Ltd., DIC-PPS LDlOpl l was used as the aromatic polymer compound.
  • the polymer film was used. 1 Weigh 121 g of chlorobutane and 3.6 g of chlorosulfonic acid. 3. Prepare a polymer electrolyte membrane in the same manner as in Example 17 except that an Owt% chlorosulfonic acid solution is prepared and the polymer film is 0.28 g. (The amount of chlorosulfonic acid added was 12.9 times the weight of the polymer film). The results are shown in Table 3.
  • Example 24 A polymer film obtained in the same manner as in Example 24 was used. Polymer electrolyte membrane in the same manner as in Example 23, except that 851 g of dichloromethane and 8.5 g of chlorosulfonic acid were weighed, and 1. Owt% chlorosulfonic acid solution was prepared and the polymer film was changed to 2. Og. Got. The results are shown in Table 3.
  • high-density polyethylene manufactured by Mitsui Engineering Co., Ltd., HI-Z EX 3300F
  • Polyphenylene sulfide manufactured by Dainippon Ink Industries, Ltd., DIC-PPS LDlOpl l
  • aromatic polymer compound was used as the aromatic polymer compound.
  • the polymer film was used. 1 Weigh 136 g of chlorobutane and 2.7 g of chlorosulfonic acid. 2. Prepare a polymer electrolyte membrane in the same manner as in Example 17 except that an Owt% chlorosulfonic acid solution is prepared and the polymer film is 0.32 g. (The amount of chlorosulfonic acid added was 8.6 times the weight of the polymer film). The results are shown in Table 3.
  • Example 26 A polymer film obtained in the same manner as in Example 26 was used. 1 Weigh 14 g of chlorobutane and 4.2 g of chlorosulfonic acid, 3. Proton conductivity in the same manner as in Example 17 except that an Owt% chlorosulfonic acid solution is prepared and the high molecular weight film is 0.33 g. A conductive polymer electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 12.9 times the weight of the polymer film). The results are shown in Table 3.
  • Example 26 A polymer film obtained in the same manner as in Example 26 was used.
  • a polymer electrolyte membrane was prepared in the same manner as in Example 23 except that 875 g of dichloromethane and 4.4 g of chlorosulfonic acid were weighed to prepare a 0.5 wt% chlorosulfonic acid solution and the polymer film was changed to 2. Og. Got. The results are shown in Table 3.
  • high-density polyethylene manufactured by Mitsui Engineering Co., Ltd., HI-Z EX 3300F
  • Polyphenylene sulfide manufactured by Dainippon Ink Industries, Ltd., DIC-PPS LDlOpl l
  • aromatic polymer compound was used as the aromatic polymer compound.
  • the polymer film was used. 1 Weigh 116 g of chlorobutane and 2.3 g of chlorosulfonic acid. 2. Prepare a polymer electrolyte membrane in the same way as in Example 17 except that an Owt% chlorosulfonic acid solution is prepared and the polymer film is 0.27 g. (The amount of chlorosulfonic acid added was 8.6 times the weight of the polymer film). The results are shown in Table 3.
  • Example 29 A polymer film obtained in the same manner as in Example 29 was used. 1 Proton conductivity in the same manner as in Example 17 except that 12 g of chlorobutane and 3.6 g of chlorosulfonic acid were weighed, 3. A chlorosulfonic acid solution of Owt% was prepared, and the high molecular weight film was changed to 0.28 g. A polymer electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 12.9 times the weight of the polymer film). The results are shown in Table 3.
  • high-density polyethylene manufactured by Mitsui Engineering Co., Ltd., HI-Z EX 3300F
  • Polyphenylene sulfide manufactured by Dainippon Ink Industries, Ltd., DIC-PPS LDlOpl l
  • aromatic polymer compound was used as the aromatic polymer compound.
  • the polymer film was used. 1 114 g of chlorobutane, 2.3 g of chlorosulfonic acid Weighed and prepared a polymer electrolyte membrane in the same manner as in Example 17 except that 2.Owt% chlorosulfonic acid solution was prepared and the polymer film was changed to 0.27 g (the amount of chlorosulfonic acid added was 8.6 times the weight of the polymer film). The results are shown in Table 3.
  • Polypropylene (manufactured by Mitsui Engineering Co., Ltd., F107DV) was used as the aliphatic polymer compound.
  • poly-phenylene sulfide manufactured by Dainippon Ink & Chemicals, Inc., DIC-PPS LDlOpl was used.
  • the polymer film was used.
  • a polymer electrolyte was prepared in the same manner as in Example 17 except that 109 g of 1-chlorobutane and 4.9 g of chlorosulfonic acid were weighed to prepare a 4.5 wt% chlorosulfonic acid solution and the polymer film was changed to 0.25 g. A membrane was obtained (the amount of chlorosulfonic acid added was 19.4 times the weight of the polymer film). The results are shown in Table 3.
  • Example 32 A polymer film obtained in the same manner as in Example 32 was used. 1-Chlorobutane 103 g and chlorosulfonic acid 5.2 g were weighed, 5. Produced protons in the same manner as in Example 17 except that an Owt% chlorosulfonic acid solution was prepared and the high molecular weight film was changed to 0.24 g. A conductive polymer electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 21.6 times the weight of the polymer film). The results are shown in Table 3.
  • the polymer film was used. 1-chlorobutane ll lg, 4.4 g of chlorosulfonic acid was weighed, 4. Owt% chlorosulfonic acid solution was prepared, and the polymer film was changed to 0.26 g. An electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 17.3 times the weight of the polymer film). The results are shown in Table 3.
  • Example 34 A polymer film obtained in the same manner as in Example 34 was used. 1-Chlorobutane 12 2 g and chlorosulfonic acid 5.5 g were weighed, a 4.5 wt% chlorosulfonic acid solution was prepared, and proton conduction was performed in the same manner as in Example 17 except that the high molecular weight film was changed to 0.28 g. A polymer electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 19.4 times the weight of the polymer film). The results are shown in Table 3.
  • Example 34 A polymer film obtained in the same manner as in Example 34 was used. 1-Chlorobutane 11 9 g, chlorosulfonic acid 6. Og was weighed, 5. Owt% chlorosulfonic acid solution was prepared, and proton conduction was performed in the same manner as in Example 17 except that the high molecular weight film was changed to 0.28 g. A conductive polymer electrolyte membrane was obtained (the amount of chlorosulfonic acid added was 21.6 times the weight of the polymer film). The results are shown in Table 3.
  • Polyphenylene sulfide (Dainippon Ink Industries Ltd.) as an aromatic polymer A company-made DIC—PPS LDlOpl l) was used.
  • pellets of the aromatic polymer compound were melt-extruded with an extruder in which a T-die was set in a twin-screw kneading extruder at a screw temperature of 290 ° C and a T-die temperature of 290 ° C.
  • the polymer film was used. 1 Weigh 119 g of chlorobutane and 1.2 g of chlorosulfonic acid, 1. Prepare a polymer electrolyte membrane in the same manner as in Example 17 except that an Owt% chlorosulfonic acid solution was prepared and the polymer film was 0.28 g. (The amount of chlorosulfonic acid added was 4.3 times the weight of the polymer film). The results are shown in Table 3.
  • polyphenylene sulfide manufactured by Dainippon Ink & Chemicals, Inc., DIC—PPS ML320p was used.
  • the aromatic polymer compound pellets were melt-extruded with a twin-screw kneading extruder with a T-die set under conditions of a screw temperature of 290 ° C and a T-die temperature of 290 ° C. A molecular film was obtained.
  • the polymer film was used. 1 Polymer electrolyte membrane in the same manner as in Example 17 except that 128 g of chlorobutane and 1.9 g of chlorosulfonic acid were weighed to prepare a 1.5 wt% chlorosulfonic acid solution and the polymer film was changed to 0.30 g. (The amount of chlorosulfonic acid added was 6.5 times the weight of the polymer film). The results are shown in Table 3.
  • the proton conductive polymer electrolyte membrane of the present invention has proton conductivity in the same order as that of the conventional polymer electrolyte membrane. It was revealed that it is useful as a polymer electrolyte membrane.
  • the polymer electrolyte membrane of the present invention is more than the conventional polymer electrolyte membrane. It is clear that the methanol permeation coefficient is low and that it shows a high methanol barrier coefficient. It was shown to be useful as a polymer electrolyte membrane for batteries.
  • FIG. 1 is a cross-sectional view of a main part of a polymer electrolyte fuel cell (direct methanol fuel cell) of the present invention.
  • FIG. 2 is a cross-sectional view of a main part of a direct methanol fuel cell according to the present invention.
  • FIG. 3 is a transmission electron microscope image of a cross section of the polymer film of the present invention (Example 1).
  • FIG. 4 is a transmission electron microscope image of a cross section of the polymer film of the present invention (Example 2).
  • FIG. 5 is a transmission electron microscope image of a cross section of the polymer film of the present invention (Example 3).
  • FIG. 6 is a transmission electron microscope image of a cross section of the polymer film of the present invention (Example 4).
  • FIG. 7 is a transmission electron microscope image of a cross section of the polymer film of the present invention (Example 5).
  • FIG. 8 is a transmission electron microscope image of a cross section of the polymer film of the present invention (Example 6).
  • FIG. 9 is a transmission electron microscope image of a cross section of the polymer film of the present invention (Example 7).
  • FIG. 10 is a transmission electron microscope image of a cross section of the polymer film of the present invention (Example 8).
  • FIG. 11 is a transmission electron microscope image of a cross section of the polymer film of the present invention (Example 9).
  • FIG. 12 is a transmission electron microscope image of a cross section of the polymer film of the present invention (Example 10).
  • FIG. 13 is a cross-sectional view of a main part of a solid polymer fuel cell (direct methanol fuel cell) of the present invention.
  • FIG. 14 is an embodiment of a cross-sectional view of the main part of the direct methanol fuel cell of the present invention.
  • FIG. 15 shows the results of evaluation of power generation characteristics of a direct methanol fuel cell in Example 23 of the present invention.
  • FIG. 16 is a result of evaluation of power generation characteristics of a direct methanol fuel cell in Example 25 of the present invention.
  • FIG. 17 shows the evaluation results of power generation characteristics of a direct methanol fuel cell in Example 28 of the present invention.
  • a polymer electrolyte membrane having at least two kinds of compound power that is, an aliphatic polymer compound and an aromatic polymer compound containing a proton conductive group. It became possible to express a high methanol barrier property. These have excellent proton conductivity and high methanol barrier properties, and are useful as polymer electrolyte membranes for polymer electrolyte fuel cells, direct liquid fuel cells, and direct methanol fuel cells. Further, the polymer electrolyte membrane can be realized by using the polymer film of the present invention as a material.
  • At least three kinds of polymer compounds including a polymer compound having an aromatic unit, a thermoplastic elastomer, and a polymer compound having no aromatic unit are included as essential components.
  • High molecular electrolyte membranes in which proton conductive groups are introduced into aromatic units in polymer films, have excellent proton conductivity and high methanol barrier properties, such as solid polymer fuel cells and direct liquid fuels. It is useful as a polymer electrolyte membrane for batteries and direct methanol fuel cells. Further, by using the polymer film of the present invention as a material, It became possible to realize a molecular electrolyte membrane.
  • At least two kinds of polymer compounds that is, a polymer compound having an aromatic unit and a polymer compound having no aromatic unit are included,

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Abstract

Est présentée une membrane d'électrolyte de polymère utile comme constituant d'une pile à combustible de polymère solide, une pile à combustible de liquide direct ou une pile à combustible méthanol direct. Sont également présentés un film de polymère comme matériau pour cette membrane d'électrolyte de polymère, un procédé de production d'une membrane d'électrolyte et une pile à combustible de polymère solide utilisant une membrane d'électrolyte. Sont également présentés une membrane d'électrolyte de polymère présentant une excellente conductivité des protons et des propriétés élevées de barrière au méthanol, servant de constituant d'une pile à combustible de polymère solide, une pile à combustible de liquide direct ou une pile à combustible méthanol direct, et enfin un procédé de production, comme une membrane d'électrolyte de polymère. Sont aussi présentés un film de polymère comme matériau pour cette membrane d'électrolyte de polymère et un procédé de production de ce film de polymère. Est précisément présenté un « film de polymère contenant essentiellement un composé polymère (A) ayant une unité aromatique et un composé de polymère (B) n'ayant pas d'unité aromatique ». Est enfin spécifiquement présenté un « film polymère contenant aussi un élastomère thermoplastique (C) comme autre composant essentiel ».
PCT/JP2005/014730 2004-08-20 2005-08-11 Membrane d'électrolyte de polymère, film de polymère comme matériau pour celle-ci, procédé de production de membrane d'électrolyte et pile à combustible en polymère solide utilisant ladite membrane d'électrolyte WO2006019029A1 (fr)

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JP2008021627A (ja) * 2006-06-15 2008-01-31 Kaneka Corp 高分子電解質膜の製造方法、並びに当該製造方法によって製造された高分子電解質膜およびその利用
JP2008112648A (ja) * 2006-10-31 2008-05-15 Kaneka Corp 膜電極接合体、およびその製造方法、並びに燃料電池
EP2264087A4 (fr) * 2008-03-26 2012-08-29 Teijin Ltd Film de renforcement d'une membrane électrolyte d'une pile à combustible polymère solide
CN113943451A (zh) * 2020-07-15 2022-01-18 大韩油化株式会社 高分子电解质膜及其制造方法

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JP2003017090A (ja) * 2001-07-03 2003-01-17 Sumitomo Chem Co Ltd 高分子電解質膜およびそれを用いた燃料電池
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