WO2005119822A1 - Film polyélectrolytique pour cellule électrochimique de type polymère solide - Google Patents

Film polyélectrolytique pour cellule électrochimique de type polymère solide Download PDF

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Publication number
WO2005119822A1
WO2005119822A1 PCT/JP2005/009931 JP2005009931W WO2005119822A1 WO 2005119822 A1 WO2005119822 A1 WO 2005119822A1 JP 2005009931 W JP2005009931 W JP 2005009931W WO 2005119822 A1 WO2005119822 A1 WO 2005119822A1
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polymer electrolyte
fuel cell
electrolyte membrane
polymer
sulfonic acid
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PCT/JP2005/009931
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English (en)
Japanese (ja)
Inventor
Tetsuji Hirano
Tatsuya Arai
Masayuki Kinouchi
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Ube Industries, Ltd.
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Publication of WO2005119822A1 publication Critical patent/WO2005119822A1/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
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/126—Copolymers block
    • 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
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones
    • 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

Definitions

  • the present invention relates to a polymer electrolyte membrane having improved alcohol permeation resistance, which is used for a polymer electrolyte fuel cell.
  • the polymer electrolyte fuel cell using the polymer electrolyte membrane of the present invention has features such as high power generation efficiency, low pollution and low noise.
  • Patent Document 1 JP-A-10-21943
  • Patent Document 2 JP-A-10-45913
  • Patent Document 3 Japanese Patent Application Laid-Open No. 11-116679
  • Patent Document 4 JP-A-11-67224
  • Patent Document 5 JP-A-2003-31232
  • An object of the present invention is to provide a polyethersulfone-based solid polymer fuel into which a sulfonic acid group is introduced, which is inexpensive, durable, and has low alcohol permeability while maintaining high proton conductivity.
  • An object of the present invention is to provide a polymer electrolyte membrane for a battery.
  • the inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a hydrophilic segment having a sulfonic acid group having a naphthalene group and a sulfonic acid group have not been introduced.
  • the present inventors have found that by using a polyethersulfone-based block copolymer comprising a hydrophobic segment, a high molecular weight electrolyte membrane having improved alcohol resistance can be obtained while maintaining high proton conductivity. Reached.
  • the present invention provides "a hydrophilic segment containing a sulfonic acid group and a hydrophobic segment not containing a sulfonic acid group, wherein the hydrophilic segment is a structural unit represented by the following chemical formula (1).
  • a polymer electrolyte membrane for a polymer electrolyte fuel cell comprising an aromatic polyethersulfone block copolymer having a structure in which a sulfonic acid group is introduced as a substituent.
  • the present invention provides a "polymer electrolyte membrane for a polymer electrolyte fuel cell, wherein the hydrophobic segment has a structure represented by the following chemical formula (2) in the polymer electrolyte membrane for a polymer electrolyte fuel cell".
  • the hydrophobic segment has a structure represented by the following chemical formula (2) in the polymer electrolyte membrane for a polymer electrolyte fuel cell.
  • n represents an integer of 3 to: 1500, preferably an integer of 5 to 1000.
  • the present invention also provides a polymer electrolyte membrane for a solid polymer fuel cell, wherein the aromatic polyethersulfone block copolymer has an ion exchange capacity of 0.8 meq / g to 2.
  • the present invention provides a polymer electrolyte membrane for a polymer electrolyte fuel cell, wherein the weight fraction of the hydrophilic segment in the aromatic polyethersulfone block copolymer is determined by the following formula:
  • the present invention provides a “polymer electrolyte membrane for a polymer electrolyte fuel cell having a range of 0.2 to 0.8”.
  • the present invention provides a polymer electrolyte membrane for a polymer electrolyte fuel cell, wherein, when a membrane is used, a methanol permeation coefficient P between a 10% by weight methanol aqueous solution and water, which is obtained by the following equation, is obtained. , and the at 30 ° C 1. 0 X 10- 6 (cm 2 / sec) or less, for 1. 5 X 10- 6 (cm 2 / sec) a polymer electrolyte fuel cell is below at 60 ° C A polymer electrolyte membrane.
  • the present invention provides a polymer electrolyte for a polymer electrolyte fuel cell as the electrolyte membrane.
  • a polymer electrolyte fuel cell characterized by using a membrane.
  • the present invention provides a “direct alcohol fuel cell characterized by using the polymer electrolyte membrane for a solid polymer fuel cell as the electrolyte membrane”.
  • FIG. 1 is a graph showing the temperature dependence of the methanol permeability coefficient of the polymer electrolyte membranes of the examples and comparative examples, wherein the vertical axis represents the methanol permeability coefficient and the horizontal axis represents the reciprocal of the temperature. Best mode for implementing
  • the aromatic polyethersulfone block copolymer used in the present invention is not particularly limited in its synthesis method, and can be synthesized by, for example, the following methods (1) and (2). There is no restriction on the position or number of sulfonic acid groups to be introduced.
  • the prepolymer of the hydrophobic segment used for the synthesis of the aromatic polyether sulfone block copolymer and the prepolymer of the hydrophilic segment into which the sulfonic acid group is introduced or the hydrophilic segment into which the sulfonic acid group is not introduced are used.
  • Prepolymers are well known as aromatic polyethersulfones and are disclosed, for example, in RN Johnson et al., J. Polym. ScL, Al, Vol. 5, 2375 (1967), Japanese Patent Publication No. 46-21458. As described above, it can be synthesized by reacting a dialkali metal salt of divalent phenol with an aromatic dihalide.
  • examples of the aromatic dihalides used for synthesizing the prepolymer of each segment described above include bis (4-chlorophenyl) sulfone, bis (4-fluorophenylnore) snolephone, and bis ( 4 _Bromopheninole sunorehon, bis (4 phenodofenore) snorehon, bis (2-chlorophenylinore) snorehon, bis (2-phenolenofinorenole) sunorehon, bis (2_methyl_4_cloguchiphenyl) Sulfone and the like can be mentioned, alone or in two kinds The above may be used in combination. Of these, preferred are bis (4-chlorophenyl) sulfone and bis (4-fluorophenyl) sulfone.
  • the divalent phenol used for the synthesis of the prepolymer of the hydrophilic segment into which the sulfonic acid group is introduced or the prepolymer of the hydrophilic segment into which the sulfonic acid group is not introduced is, for example, 1 Dihydroxynaphthalene compounds such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 1,8-dihydroxynaphthalene. They may be used in combination. If necessary, some of the divalent phenols described below may be combined.
  • examples of the divalent phenol used for synthesizing the prepolymer of the hydrophobic segment include hydroquinone, resorcinol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxy Naphthalene, 2,7 dihydroxynaphthalene, 4,4'-biphenol, 2,2'-biphenol, bis (4-hydroxyphenyl) ether, bis (2-hydroxyphenyl) ether, 2,2-bis (4-hydroxyphenyl) ) Propane, 2,2 bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenylinole) propane, bis (4-hydroxyphenyl) methane, bis ( 4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) Nyl) ketone, 2,2 bis (3,5 dimethyl-14 hydroxyphenyl) hexafluoroprop
  • the degree of polymerization of the prepolymer of each segment described above is preferably in the range of 3 to 1500, and more preferably in the range of 5 to 1000. If the degree of polymerization is less than 3, the properties of the block copolymer synthesized using the prepolymer are difficult to exhibit, while if the degree of polymerization exceeds 1500, the synthesis of the block copolymer is difficult. Become.
  • hydrophobic segment prepolymer is one having the structure of the following chemical formula (2).
  • n represents an integer of 3 to: 1500, preferably an integer of 5 to 1000.
  • the prepolymer of the hydrophobic segment and the prepolymer of the hydrophilic segment having no sulfonic acid group may be a commercially available polymer having the corresponding structure.
  • RN Johnson et al., J. Polym. Sci., A_l, Vol. 5, 2375 (1967) The synthesis conditions of polyethersulfone described in JP-B-46-21458. Under the same conditions, those having a controlled molecular weight and terminal group by ether exchange reaction may be used.
  • both ends can be synthesized by reacting a prepolymer of a phenol alkali metal salt terminal group segment by a similar method using a linking agent.
  • a linking agent include the above-mentioned aromatic dihalides, and preferably a highly reactive “aromatic dihalide in which halogen is fluorine”.
  • a polyethersulfone Z polythioethersulfone block copolymer it can be synthesized by the method disclosed in JP-A-61-168629.
  • hydrophobic segment prepolymer having the structure of the above chemical formula (2) when a hydrophobic segment prepolymer having the structure of the above chemical formula (2) is used, as disclosed in JP-A-2003-206354, a hydrophilic segment having a phenol alkali metal salt terminal group is used. It is possible to synthesize a prepolymer with a commercial hydrophobic segment prepolymer by simply reacting the solution in a solution at a temperature of 120 ° C to 200 ° C.
  • a method for introducing a sulfonic acid group into polyether sulfone is known, and a block copolymer having no sulfonic acid group introduced therein can be used, for example, in Japanese Patent Application Laid-Open Nos. 61-36781 and 1-54323.
  • the reaction is carried out at 95 ° C to 98% by weight of concentrated sulfuric acid for 0.2 hours to 96 hours at 10 ° C to 80 ° C.
  • a sulfonic acid group can be introduced only into the hydrophilic segment, and the aromatic polyether sulfone block copolymer used in the present invention can be obtained.
  • the aromatic polyethersulfone block copolymer used in the present invention is synthesized from a prepolymer of a hydrophilic segment into which a sulfonic acid group is introduced and a prepolymer of a hydrophobic segment, a sulfonic acid group is introduced.
  • the prepolymer of the hydrophilic segment is reacted with the prepolymer of the hydrophobic segment in the same manner as in the above-mentioned synthesis of the block copolymer having no sulfonic acid group, thereby obtaining the aromatic polyether used in the present invention.
  • a sulfone block copolymer can be obtained.
  • aromatic dihalide having a sulfonic acid group introduced therein such as bis (4-chloro-1-sulfobenzene) sulfone or bis (4-fluoro-13-sulfobenzene) sulfone, and the aforementioned dihydroxynaphthalene conjugate.
  • the aromatic polyether sulfone used in the present invention can also be obtained by synthesizing a prepolymer of a hydrophilic segment into which a sulfonate group is introduced by the above-mentioned method and then copolymerizing the same.
  • a lock copolymer can be obtained.
  • the weight fraction Fa of the hydrophilic segment determined by the following formula is preferably in the range of 0.2 to 0.8. Les, more preferably in the range of 0.3 to 0.7. When the weight fraction Fa is less than 0.2, the proton conductivity decreases, while when the weight fraction Fa is greater than 0.8, the block copolymer becomes water-soluble, which is undesirable. .
  • FIG. F ⁇ _ W _2
  • the aromatic polyether sulfone block copolymer used in the present invention preferably has an ion exchange capacity in the range of 0.8 meq / g to 2.0 meq Zg.
  • Equivalent Zg ⁇ It is more preferably in the range of 1.9 meq Zg.
  • the ion exchange capacity is less than 0.8 milliequivalents / g, the proton conductivity is low.
  • the ion exchange capacity is more than 2.0 milliequivalents / g, the block copolymer becomes water-soluble. Is not preferred.
  • the aromatic polyether sulfone block copolymer used in the present onset Ming preferably not less 50 ° C, the proton conductivity of force at a relative humidity of 9 0% 1 X 10- 2 S / cm or more members 1. it is particularly preferably 5 X 10- 2 S / cm or more.
  • the proton conductivity is lower than 1 X 10- 2 S / cm, undesirable since it lowers the power generation characteristics.
  • the method for forming the aromatic polyethersulfone block copolymer obtained as described above as the polymer electrolyte membrane for a polymer electrolyte fuel cell of the present invention is not particularly limited.
  • Aromatic polyethersulfone block copolymers such as dimethyl sulfoxide, sulfolane, N-methyl 2-pyrrolidone, 1,3-dimethyl-12-imidazolidinone, N, N dimethylformamide, N, N dimethylacetamide,
  • a film is formed by dissolving in a polar solvent such as diphenylsulfone, casting the solution on a support, and evaporating and removing the polar solvent.
  • the film thickness is 5 to 200 xm, preferably 10 to 150 xm. If the film thickness is less than 5 zm, it is difficult to handle the film, and if the film thickness is more than 200 zm, the power generation efficiency of a fuel cell decreases, which is not preferable.
  • the methanol permeability coefficient between the 10% by weight aqueous methanol solution and water is determined by the following equation.
  • C 1. is a 0 X 10- 6 (cm 2 / sec) or less, the force preferably 1. 5 X 10- 6 (cm 2 / sec) or less at 60 ° C, further, 0 in 30 ° C . 8 X 10- 6 (cm 2 / ⁇ ) or less, 60 ° C at 1. 3 X 10- 6 (cm 2 / sec) it is particularly preferred instrument less, 0 30 ° C. 8 X 10- 6 (cm 2 / sec) or less, it is preferable 1. or less 2 X 10- 6 (cm 2 / sec) at 60 ° C.
  • a part of the sulfonic acid group may be a metal salt as long as the characteristics of the present invention are not impaired.
  • it can be reinforced with a fiber, a porous membrane, or the like.
  • an inorganic acid such as phosphoric acid, hypophosphorous acid, sulfuric acid or a salt thereof, a perfluoroalkylsulfonic acid having 1 to 14 carbon atoms or a salt thereof, or a salt having 1 to 14 carbon atoms.
  • Inorganic substances such as perfluoroalkylcarboxylic acids or salts thereof, platinum, silica gel, silica, zeolite, and other polymers can also be blended.
  • the polymer electrolyte fuel cell of the present invention uses the above-described polymer electrolyte membrane of the present invention as an electrolyte membrane, and is preferably a direct alcohol fuel cell.
  • the polymer electrolyte fuel cell of the present invention can be manufactured by a known method that does not particularly limit the manufacturing method.
  • a Teflon (registered trademark) plate having a slit of 1.9 mm width and 10 mm length in which a platinum wire is attached (interval: 2 mm) across the slit, in a thermo-hygrostat; A film (width 5 mm x length 20 mm) is sandwiched between the flat plate and the platinum wire at a 90-degree angle with the platinum wire, and a 3532 LCR HiTester manufactured by Hioki Electric Co., Ltd. Was used to determine proton conductivity by complex impedance measurements.
  • the sample was stirred at room temperature for 16 hours in an aqueous sodium hydroxide solution having a clear content, and then filtered.
  • the amount of sodium hydroxide consumed was determined by titrating the filtrate with a 0.01N hydrochloric acid aqueous solution, and the ion exchange capacity was calculated.
  • a polymer electrolyte membrane is sandwiched (effective area: 5 cm 2 ) in a glass cell for membrane permeation experiments with an external heat insulation jacket, 50 ml of a 10% by weight aqueous methanol solution is placed on one side, and 50 ml of water is placed on the other side.
  • the time-dependent change in the amount of methanol permeated to the water side was measured by gas chromatography.
  • the methanol permeability coefficient P was calculated by the following equation.
  • the measurement was performed using d_DMSO as a solvent, using EX-400WB manufactured by JEOL Ltd.
  • This solution was added to the polymer solution A and stirred at 170 ° C. for 1.5 hours.
  • the solution was poured into a large amount of water to precipitate a white solid, which was separated by filtration.
  • the obtained solid was washed twice in hot water and once in methanol to obtain a block polymer PN.
  • the reduced viscosity ⁇ sp of the obtained block polymer PN was 0.68.
  • Figure 1 shows the temperature dependence of the methanol permeability coefficient of the polymer SPN membrane.
  • the graph plotted with a circle in FIG. 1 shows the polymer SPN 4 is a graph showing the temperature dependence of the methanol permeability coefficient of the membrane. Solid circles indicate the case where a 10% by weight aqueous methanol solution was used, and open circles indicate the case where a 30% by weight aqueous methanol solution was used.
  • a block polymer PBP was obtained in the same manner as in Example 1 except that 14 g of 4,4-biphenol was used instead of 12 g of 2,7-dihydroxynaphthalene.
  • the reduced viscosity ⁇ sp of the obtained block polymer P BP was 0.71.
  • a polymer SPBP film was formed in the same manner as in Example 1 to obtain a polymer SPBP film having a thickness of 50 ⁇ m. After washing with water was carried out twice, 50 ° protons conductivity of the polymer SPBP film measured at 90% relative humidity in C, 4. a 0 X 10- 2 S N m. Further, the methanol permeation coefficient ⁇ polymer SPBP film or, 30 o C in 0. 6 X 10- 6 cm 2 / ⁇ was 1. 7 X 10- 6 cm 2 / ⁇ at 60 o C.
  • Figure 1 shows the temperature dependence of the methanol permeability coefficient of the polymer SPBP membrane.
  • the graph plotted by the square in FIG. 1 is a graph showing the temperature dependence of the methanol permeability coefficient of the polymer SPBP membrane.
  • the black squares indicate the case where a 10% by weight aqueous methanol solution was used, and the white squares indicate the case where a 30% by weight aqueous methanol solution was used.
  • Nafuion 1135 Measurement of the methanol permeation coefficient (US Dupont Co.), was 2. 1 X 10- 6 cm 2 / sec, 4. 6 X 10- 6 cm 2 / sec at 60 ° C at 30 ° C Was.
  • Figure 1 shows the temperature dependence of the methanol permeability coefficient of Naphion 1135.
  • the graph plotted with diamonds in FIG. 1 is a graph showing the temperature dependence of the methanol permeability coefficient of Nafion 1135.
  • the black diamond indicates the case where a 10% by weight aqueous methanol solution was used, and the white diamond indicates the case where a 30% by weight aqueous methanol solution was used.
  • Example 2 Example 2
  • Example 2 The above gas diffusion electrode and the polymer SPN film obtained in Example 1 were joined by a hot press at 130 ° C. and 2 MPa for 1 minute to obtain an MEA.
  • the MEA obtained above was incorporated into a fuel cell manufactured by Electrochem (USA) with an electrode area of 5 cm 2 .
  • a 3 mol / l aqueous methanol solution was supplied to the anode for 100 mmlZ at a cell temperature of 60 ° C, and oxygen (humidification temperature of 50 ° C) was supplied to the power source to generate power.
  • oxygen humidity temperature of 50 ° C
  • an output of 80 mWZcm 2 was obtained at a current density of 300 mAZcm 2 .
  • the polymer electrolyte membrane of the present invention is a polyether sulfone-based polymer into which a sulfonic acid group is introduced, which is inexpensive, durable, and has reduced alcohol permeability while maintaining high proton conductivity. It is an electrolyte membrane.
  • the polymer electrolyte fuel cell of the present invention using the polymer electrolyte membrane has features such as high power generation efficiency, low pollution and low noise.

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Abstract

Il est prévu un film polyélectrolytique pour cellules électrochimiques de type polymère solide, caractérisé en ce qu’il comprend un copolymère bloc de polyéther sulfone aromatique contenant un segment hydrophile englobant des groupes sulfonés et un segment hydrophobe ne contenant pas de groupe sulfoné, le segment hydrophile ayant une structure comprenant des unités structurelles représentées par la formule chimique suivante (1) et des groupes sulfonés introduits dans celle-ci comme éléments substitutifs. [Formule chimique 1] (1)
PCT/JP2005/009931 2004-06-01 2005-05-31 Film polyélectrolytique pour cellule électrochimique de type polymère solide WO2005119822A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007119868A1 (fr) * 2006-04-13 2007-10-25 Sumitomo Chemical Company, Limited Méthode de production de membrane électrolyte polymère, membrane électrolyte polymère et pile à combustible directe au méthanol
JP2007305571A (ja) * 2006-04-13 2007-11-22 Sumitomo Chemical Co Ltd 高分子電解質膜の製造方法、高分子電解質膜及び直接メタノール型燃料電池
WO2008004645A1 (fr) * 2006-07-04 2008-01-10 Sumitomo Chemical Company, Limited Émulsion d'électrolyte polymère et utilisation de celle-ci
JP2009252471A (ja) * 2008-04-04 2009-10-29 Hitachi Ltd 燃料電池用固体高分子電解質
JP2014044220A (ja) * 2008-03-11 2014-03-13 Sumitomo Chemical Co Ltd 高分子化合物膜の判別方法

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JPH1021943A (ja) * 1996-06-28 1998-01-23 Sumitomo Chem Co Ltd 燃料電池用高分子電解質及び燃料電池
JPH11116679A (ja) * 1997-10-16 1999-04-27 Sumitomo Chem Co Ltd 高分子電解質、高分子電解質膜、及び燃料電池
JP2003031232A (ja) * 2001-05-08 2003-01-31 Ube Ind Ltd 固体高分子型燃料電池用高分子電解質及び燃料電池
JP2004031307A (ja) * 2001-11-29 2004-01-29 Ube Ind Ltd 高分子電解質組成物

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JPH1021943A (ja) * 1996-06-28 1998-01-23 Sumitomo Chem Co Ltd 燃料電池用高分子電解質及び燃料電池
JPH11116679A (ja) * 1997-10-16 1999-04-27 Sumitomo Chem Co Ltd 高分子電解質、高分子電解質膜、及び燃料電池
JP2003031232A (ja) * 2001-05-08 2003-01-31 Ube Ind Ltd 固体高分子型燃料電池用高分子電解質及び燃料電池
JP2004031307A (ja) * 2001-11-29 2004-01-29 Ube Ind Ltd 高分子電解質組成物

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007119868A1 (fr) * 2006-04-13 2007-10-25 Sumitomo Chemical Company, Limited Méthode de production de membrane électrolyte polymère, membrane électrolyte polymère et pile à combustible directe au méthanol
JP2007305571A (ja) * 2006-04-13 2007-11-22 Sumitomo Chemical Co Ltd 高分子電解質膜の製造方法、高分子電解質膜及び直接メタノール型燃料電池
WO2008004645A1 (fr) * 2006-07-04 2008-01-10 Sumitomo Chemical Company, Limited Émulsion d'électrolyte polymère et utilisation de celle-ci
JP2014044220A (ja) * 2008-03-11 2014-03-13 Sumitomo Chemical Co Ltd 高分子化合物膜の判別方法
JP2009252471A (ja) * 2008-04-04 2009-10-29 Hitachi Ltd 燃料電池用固体高分子電解質

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