WO2007102418A1 - Membrane electrolyte polymere solide pour pile a combustible et pile a combustible - Google Patents

Membrane electrolyte polymere solide pour pile a combustible et pile a combustible Download PDF

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Publication number
WO2007102418A1
WO2007102418A1 PCT/JP2007/054011 JP2007054011W WO2007102418A1 WO 2007102418 A1 WO2007102418 A1 WO 2007102418A1 JP 2007054011 W JP2007054011 W JP 2007054011W WO 2007102418 A1 WO2007102418 A1 WO 2007102418A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte membrane
solid polymer
polymer electrolyte
fuel cell
graft
Prior art date
Application number
PCT/JP2007/054011
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English (en)
Japanese (ja)
Inventor
Junichi Tsukada
Toshio Ohba
Nobuo Kawada
Original Assignee
Shin-Etsu Chemical Co., Ltd.
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Filing date
Publication date
Application filed by Shin-Etsu Chemical Co., Ltd. filed Critical Shin-Etsu Chemical Co., Ltd.
Publication of WO2007102418A1 publication Critical patent/WO2007102418A1/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
    • C08J5/2287—After-treatment
    • C08J5/2293—After-treatment of fluorine-containing membranes
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • 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
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • 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]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid polymer electrolyte membrane for a fuel cell and a fuel cell.
  • Fuel cells using solid polymer electrolyte type ion exchange membranes have been widely put into practical use as power sources for electric vehicles and simple auxiliary power sources because of their high energy density, with operating temperatures as low as 100 ° C or lower. Expected.
  • this fuel cell there are important elemental technologies relating to solid polymer electrolyte membranes, platinum-based catalysts, gas diffusion electrodes, and polymer electrolyte membrane-electrode assemblies.
  • solid polymer electrolyte membranes with good characteristics as fuel cells is one of the most important technologies.
  • electrolyte membrane fuel cell gas diffusion electrodes are combined on both sides of the electrolyte membrane, and the membrane and the electrode have a substantially integrated structure.
  • the electrolyte membrane acts as an electrolyte for conducting protons, and also has a role as a diaphragm for preventing hydrogen or methanol as a fuel and an oxidizing agent from being directly mixed even under pressure.
  • Such an electrolyte membrane is required to have a high proton exchange rate and high ion exchange capacity as an electrolyte, and a constant and high water holding capacity in order to keep electric resistance low.
  • fluororesin-based electrolyte membranes such as “Nafion” have excellent chemical durability and stability, but in direct methanol fuel cells (D MFC) using methanol as fuel, methanol Causes a crossover phenomenon that passes through the electrolyte membrane, resulting in low output There was a problem. Furthermore, since the fluororesin-based electrolyte membrane starts from the synthetic ability of the monomer, it has a problem in that it requires a large number of manufacturing steps and increases the cost, which is a major obstacle to practical use.
  • D MFC direct methanol fuel cells
  • styrene Z dibutene benzene co-graft membranes that are co-graft polymerized by simultaneously charging two or more types of graft raw materials such as styrene and dibutene benzene and fluorine resin irradiated with radiation are: Although proton conductivity is equivalent to or higher than that of “naphth ion” and methanol permeability is lower than that of “naphth ion”, an electrolyte membrane can be obtained, but further reduction of methanol permeability is required.
  • an object of the present invention is to provide a solid polymer electrolyte membrane and a fuel cell produced by a radiation graft polymerization method and having both high proton conductivity and low methanol permeability.
  • the present inventors have found that the polymerizable monomer is adjusted so that the number of graft chain units is 30 or less on the resin film irradiated with radiation. It is found that a solid polymer electrolyte membrane having both high proton conductivity and low methanol permeability can be obtained by sulfonating after graft polymerization of the polymer. It came.
  • the present invention provides the following solid polymer electrolyte membrane for fuel cell and fuel cell.
  • a solid polymer for a fuel cell characterized in that a polymerized monomer is graft-polymerized on a resin film irradiated with radiation so that the graft chain has a Nut number of 30 or less and is sulfonated. Electrolyte membrane.
  • a fuel cell wherein the solid polymer electrolyte membrane according to claim 1 is provided between a fuel electrode and an air electrode.
  • the invention's effect [0009]
  • the solid polymer electrolyte membrane produced by the radiation grafting of the present invention exhibits high ionic conductivity and low methanol permeability. Therefore, the electrolyte membrane for fuel cells, particularly for direct methanol fuel cells. Suitable as electrolyte membrane.
  • the solid polymer electrolyte membrane for a fuel cell of the present invention is such that the number of graft chain units is 30 or less, preferably 5 to 25, more preferably 10 to 20 on the resin film irradiated with radiation.
  • the resin film polytetrafluoroethylene, tetrafluoroethylene perfluoroalkyl butyl ether copolymer is used.
  • Fluorine resin films such as tetrafluoroethylene monohexafluoropropylene copolymer and ethylene-tetrafluoroethylene copolymer, or hydrocarbon resin films such as polyethylene and polypropylene. It is done.
  • the absorbed dose of radiation applied to the resin film is increased.
  • This is possible by controlling the grafting ratio of the polymerizable monomer to a certain ratio (usually 60% or less, more preferably 20 to 50%, still more preferably 30 to 40%) after generating a large amount of radicals. become.
  • the control of the graft ratio include a method of adjusting the polymerizable monomer concentration, oxygen concentration, etc. during graft polymerization.
  • styrene monomer such as styrene, ⁇ -methylstyrene, ⁇ funoleite rostyrene, styrene sulphonic acid, sodium styrene sulphonate, and the like, which are preferably monofunctional polymerizable monomers, is desirable.
  • Acrylic monomers such as sodium acrylamidomethylpropanesulfonate can also be used alone or in appropriate combination. It is also possible to use a polyfunctional polymerizable monomer in combination.
  • Radiation graft polymerization is a method in which radicals are generated by irradiating a resin film with radiation, and a polymerizable monomer is grafted using the radical as a graft point. Radiation is preliminarily applied to the main chain of the resin film. Then, after generating radicals that will be the starting point of grafting, the pre-irradiation method in which the resin is brought into contact with the monomer to carry out the grafting reaction, and simultaneous irradiation with radiation in the coexistence of the polymerizable monomer and the resin film Although there is an irradiation method, in the present invention, A deviation method can also be adopted. In this case, the film thickness of the resin film is not particularly limited. Repulsive force 15-: LOO / zm Especially, the force of 25-60 / zm is preferable!
  • Examples of the radiation irradiated for graft polymerization in the present invention include ⁇ -rays, X-rays, electron beams, ion beams, ultraviolet rays, and the like.
  • ⁇ -rays and electrons are used because of the ease of radical generation. Lines are preferred.
  • the absorbed dose of radiation is greater than or equal to lOkGy.
  • the absorbed dose is 20 to 300 kGy, and more desirably, the absorbed dose is 150 to 250 kGy. If it is less than 10 kGy, the number of monomer units in the graft chain must be increased in order to obtain the desired ionic conductivity with less radical generation. If it exceeds 300 kGy, the mechanical properties such as elongation and strength of the resin film may deteriorate.
  • the irradiation with radiation is preferably performed in an inert gas atmosphere such as helium, nitrogen, and argon gas.
  • the oxygen concentration in the gas is preferably lOOppm or less, particularly preferably 50ppm or less. There is no need to do this in the absence of oxygen.
  • the amount of polymerizable monomer grafted on the irradiated resin is 100 mass% of the resin final, whereas the polymerization '14 monomer is 1,000,000 to 100,000 mass%. It is preferable to use 4,000 to 20,000 parts by mass. If the amount of the monomer is too small, the contact may be insufficient. If the amount is too large, the monomer may not be used efficiently.
  • a polymerization initiator such as azobisisoptyl-tolyl may be appropriately used as long as the object of the present invention is not impaired.
  • a solvent can be used at the time of the grafting reaction, and it is preferable to use a solvent that uniformly dissolves the monomer, for example, ketones such as acetone and methyl ethyl ketone, ethyl acetate, butyl acetate and the like.
  • Esters alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, ethers such as tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, xylene, etc.
  • Aromatic hydrocarbons, aliphatic or alicyclic hydrocarbons such as n-heptane, n-hexane, and cyclohexane, or a mixed solvent thereof can be used.
  • the monomer Z solvent (mass ratio) is preferably 0.01 to 1. If the monomer Z solvent (mass ratio) is greater than 1, it will be difficult to adjust the number of monomer units in the graft chain, and if less than 0.01, The graft rate may be too low. A more desirable range is 0.03 to 0.5.
  • the reaction conditions for the graft polymerization are preferably 0 to 100 ° C, particularly 40 to 80 ° C, and 1 to 40 hours, particularly 4 to 20 hours. It can be carried out in an inert gas atmosphere such as nitrogen or argon, or at an oxygen concentration of 0.01 to 20 Vol%.
  • a solid polymer electrolyte membrane can be obtained by graft polymerization of a polymerizable monomer to a resin film irradiated with radiation and further sulfonation.
  • the grafted membrane can be introduced with chlorosulfonic acid groups by immersing it in monodichloroethane chlorosulfonate.
  • the membrane reacted with chlorosulfonic acid can be sulfonated by reacting in an aqueous solution of sodium hydroxide or sodium hydroxide to form an alkali salt of sulfonic acid, followed by acid treatment with hydrochloric acid or the like.
  • the solid polymer electrolyte membrane of the present invention can be used as a solid polymer electrolyte membrane provided between a fuel electrode and an air electrode of a fuel cell, and a catalyst layer on both sides of the solid polymer electrolyte membrane.
  • a fuel cell that is suitably used as an electrolyte membrane for a direct methanol fuel cell and excellent in battery characteristics without a methanol crossover.
  • the configuration of the fuel electrode and the air electrode, the material, and the configuration of the fuel cell can be known.
  • the number of graft chain units is the force determined by 13 CN MR.
  • EDF E ethylene-tetrafluoroethylene copolymer
  • Graft rate [(film weight after grafting-film weight before grafting) before Z grafting Film mass] ⁇ ⁇ (%)
  • the film weight after grafting was the weight after the grafted film was washed once with toluene and three times with acetone and dried under reduced pressure at 60 ° C for 2 hours.
  • the average number of styrene units per graft chain of the styrene graft chain determined by 13 C NMR was 20.
  • the graft polymerized membrane is immersed in a mixed solution of 30 g of chlorosulfonic acid and 70 g of 1,2-dichloroethane, heated at 50 ° C for 2 hours, and then immersed in a 1N aqueous solution of caustic potassium at 90 ° C for 2 hours for hydrolysis. Subsequently, after being immersed in 2N hydrochloric acid at 90 ° C. for 2 hours, it was washed 3 times with pure water to obtain a solid polymer electrolyte membrane containing sulfonic acid groups. Table 1 shows the results of measuring the characteristics of the electrolyte membrane by the following method.
  • the resistance in the longitudinal direction of the strip sample was measured at room temperature by the 4-terminal AC impedance method.
  • EDF E ethylene-tetrafluoroethylene copolymer
  • Graft rate [(film weight after grafting-film weight before grafting) Z film weight before grafting] X 100 (%)
  • the film weight after grafting was the weight after the grafted film was washed once with toluene and three times with acetone and dried under reduced pressure at 60 ° C for 2 hours.
  • the average number of styrene units per graft chain of the styrene graft chain determined by 13 C NMR was about 170.
  • the graft polymerized membrane is immersed in a mixed solution of 30 g of chlorosulfonic acid and 70 g of 1,2-dichloroethane, heated at 50 ° C for 2 hours, and then immersed in a 1N aqueous solution of caustic potassium at 90 ° C for 2 hours for hydrolysis. Subsequently, after being immersed in 2N hydrochloric acid at 90 ° C. for 2 hours, it was washed 3 times with pure water to obtain a solid polymer electrolyte membrane containing sulfonic acid groups. Table 1 shows the results of measurement by the method of Example 1 for the characteristics of this electrolyte membrane.
  • Example 1 The ethylene-tetrafluoroethylene copolymer used in Example 1 was irradiated with 0.1 g at room temperature under a nitrogen atmosphere at an acceleration voltage of 10 kV electron beams on both sides at 2 kGy each, and immediately after that, 20.0 g of styrene and dibutenebenzene were used. 2. Immerse it in a 30ml container equipped with 4g of a three-way cock, publish nitrogen for 15 minutes at room temperature, and then heat at 60 ° C for 16 hours. The graft ratio determined in the same manner as in Example 1 was 52%.
  • the graft polymerized membrane is immersed in a mixed solution of 30 g of chlorosulfonic acid and 70 g of 1,2-dichloroethane, heated at 50 ° C for 2 hours, and then immersed in a 1N aqueous solution of caustic potassium at 90 ° C for 2 hours for hydrolysis. Subsequently, after being immersed in 2N hydrochloric acid at 90 ° C. for 2 hours, it was washed 3 times with pure water to obtain a solid polymer electrolyte membrane containing sulfonic acid groups. Table 1 shows the results of measurement by the method of Example 1 for the characteristics of this electrolyte membrane.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Toxicology (AREA)
  • Materials Engineering (AREA)
  • Fuel Cell (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne une membrane électrolyte polymère solide pour piles à combustible caractérisée en ce qu'elle est obtenue par polymérisation-greffage d'un monomère polymérisable sur une couche de résine soumise à un rayonnement, de telle façon que le nombre d'unités de la chaine greffée est inférieur ou égal à 30, suivie d'une sulfonation de la couche obtenue. Comme la membrane électrolyte polymère solide produite par une telle polymérisation-greffage sous rayonnement a une forte conductivité ionique et une faible perméabilité au méthanol, elle peut servir de membrane électrolyte pour piles à combustible, en particulier comme membrane électrolyte pour les piles à combustible à méthanol direct.
PCT/JP2007/054011 2006-03-06 2007-03-02 Membrane electrolyte polymere solide pour pile a combustible et pile a combustible WO2007102418A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006059194A JP2009151938A (ja) 2006-03-06 2006-03-06 燃料電池用固体高分子電解質膜及び燃料電池
JP2006-059194 2006-03-06

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WO2007102418A1 true WO2007102418A1 (fr) 2007-09-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011076579A1 (fr) 2009-12-21 2011-06-30 Höganäs Ab (Publ) Elément de stator pour une machine à pôle modulé

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6665418B2 (ja) * 2015-03-31 2020-03-13 株式会社Ihi 電解質膜の製造方法
EP3187524A1 (fr) * 2015-12-29 2017-07-05 Sabanci Üniversitesi Membrane échangeuse de protons et son procédé de préparation
JP6872765B2 (ja) * 2016-07-22 2021-05-19 国立大学法人山口大学 モザイク荷電膜の製造方法及びモザイク荷電膜

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002313364A (ja) * 2001-04-13 2002-10-25 Hitachi Cable Ltd 燃料電池用電解質膜及びその製造方法並びに燃料電池
JP2005078871A (ja) * 2003-08-29 2005-03-24 Shin Etsu Chem Co Ltd 固体高分子電解質膜の製造方法及び燃料電池
JP2006059776A (ja) * 2004-08-24 2006-03-02 Shin Etsu Chem Co Ltd 燃料電池用固体高分子電解質膜及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002313364A (ja) * 2001-04-13 2002-10-25 Hitachi Cable Ltd 燃料電池用電解質膜及びその製造方法並びに燃料電池
JP2005078871A (ja) * 2003-08-29 2005-03-24 Shin Etsu Chem Co Ltd 固体高分子電解質膜の製造方法及び燃料電池
JP2006059776A (ja) * 2004-08-24 2006-03-02 Shin Etsu Chem Co Ltd 燃料電池用固体高分子電解質膜及びその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011076579A1 (fr) 2009-12-21 2011-06-30 Höganäs Ab (Publ) Elément de stator pour une machine à pôle modulé

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