WO2008105547A1 - Électrolyte polymère solide - Google Patents

Électrolyte polymère solide Download PDF

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Publication number
WO2008105547A1
WO2008105547A1 PCT/JP2008/053713 JP2008053713W WO2008105547A1 WO 2008105547 A1 WO2008105547 A1 WO 2008105547A1 JP 2008053713 W JP2008053713 W JP 2008053713W WO 2008105547 A1 WO2008105547 A1 WO 2008105547A1
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Prior art keywords
polymer electrolyte
solid polymer
acid
membrane
iii
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PCT/JP2008/053713
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English (en)
Japanese (ja)
Inventor
Masayuki Chokai
Hiroaki Kuwahara
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Teijin Limited
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Publication of WO2008105547A1 publication Critical patent/WO2008105547A1/fr

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    • 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
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • 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
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
    • 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 solid polymer electrolyte excellent in ion conductivity and oxidation resistance, a solid polymer electrolyte composition comprising the solid polymer electrolyte and a polymer having ion conductivity, and a solid polymer electrolyte comprising any of these.
  • the present invention relates to a molecular electrolyte membrane, a membrane Z electrode assembly using the solid polymer electrolyte membrane, and a fuel cell using the membrane Z electrode assembly.
  • a solid polymer electrolyte is a solid polymer material having an electrolyte group in the polymer chain, and has the property of selectively permeating cations or anions by firmly binding to specific ions. Therefore, it is formed into particles, fibers, or membranes and used in various applications such as electrodialysis, diffusion dialysis, and battery membranes.
  • a fuel cell is provided with a pair of electrodes on both sides of a solid polymer electrolyte membrane of ion-conducting ⁇ fe, supplying hydrogen gas or methanol as fuel to one electrode (fuel electrode), and oxygen gas or air as the oxidant To the other electrode (air electrode) to obtain an electromotive force.
  • hydrogen and oxygen are produced by electrolyzing water using a solid polymer electrolyte membrane.
  • Fluorine-based electrolyte membranes typified by sulfonic acid membranes are widely used as solid polymer electrolyte membranes for fuel cells and water electrolysis because of their excellent chemical stability.
  • Sodium chloride electrolysis produces sodium hydroxide, chlorine and hydrogen by electrolyzing a sodium chloride aqueous solution using a solid polymer electrolyte membrane.
  • the polymer electrolyte membrane is composed of chlorine and high temperature, high concentration sodium hydroxide aqueous solution. It is not possible to use hydrocarbon electrolyte membranes that are poorly resistant to these when exposed to liquids. For this reason, solid polymer electrolyte membranes for salt electrolysis are generally resistant to chlorine and high-temperature, high-concentration sodium hydroxide aqueous solution, and in addition to prevent reverse diffusion of the generated ions. Perfluorosulfonic acid membranes with partially introduced carboxylic acid groups are used.
  • the fluorine-based electrolyte typified by a perfluorinated rosulfonic acid membrane has a C 1 F bond, and thus has a very large chemical stability.
  • the above-mentioned 'for fuel cell, for water electrolysis', or salt In addition to solid polymer electrolyte membranes for electrolysis, it can also be used as solid polymer electrolyte membranes for hydrohalic acid electrolysis, and also for humidity sensors, gas sensors, oxygen concentrators, etc. using ionic conductivity Widely applied.
  • the disadvantage is that fluorine-based electrolytes are difficult to manufacture and are very expensive.
  • fluorine-based electrolyte membranes are used in limited applications such as space or military polymer electrolyte fuel cells, and are used in consumer applications such as solid polymer fuel cells as a low-pollution power source for automobiles. Application was difficult.
  • an electrolyte membrane obtained by sulfonating an aromatic hydrocarbon polymer represented by engineering plastics has been proposed as an inexpensive solid polymer electrolyte membrane.
  • aromatic hydrocarbon electrolyte membranes obtained by sulfonating these engineering plastics have the advantages of easy production and low cost. However, it has the disadvantage that it is very weak in terms of oxidation resistance.
  • Non-patent document 1 reports that, for example, sulfonated polyetheretherketone and polyethersulfone deteriorate from an ether site adjacent to sulfonic acid. From this, it is considered that when an electron donating group is present in the vicinity of the sulfonic acid, oxidative degradation starts from there. Therefore, for the purpose of improving oxidation resistance, sulfonated polyphenylene sulfone whose main chain is composed only of an electron-withdrawing group and an aromatic ring has been proposed (Patent Document 6), and sulfonic acid is introduced to the adjacent site of the sulfone group. A sulfonated polysulfone was proposed (Non-patent Document 2).
  • the degradation of the aromatic hydrocarbon electrolyte membrane is less than the oxidation degradation.
  • the sulfonic acid group strong acid which is an ion conductive substituent directly bonded to the aromatic ring, may be considered to be due to desorption at high temperatures and decrease in ionic conductivity.
  • sulfonated polyphenylene sulfone as described in Non-Patent Document 2, sulfonated polysulfone cannot avoid deterioration due to elimination of sulfonic acid.
  • Patent Document 7 proposes the use of an alkyl sulfonic acid instead of a sulfonic acid. This is effective in improving the decrease in ionic conductivity due to elimination of sulfonic acid, but the main chain of the aromatic polymer used contains an electron-donating group, which is inferior in oxidation resistance.
  • azole polymers are expected to be solid electrolyte membranes for fuel cells as polymers with excellent heat resistance and chemical resistance.
  • Patent Document 8 a sulfonated azole polymer has been reported as an azole polymer having ion conductivity (Patent Document 8).
  • Patent Documents 9 to 11 report a polybenzimidazole fuel cell electrolyte membrane obtained by obtaining a polybenzimidazole polymer using a polyphosphate.
  • Patent Document 1 JP-A-6-93114
  • Patent Document 2 Japanese Patent Laid-Open No. 9-245818
  • Patent Document 3 Japanese Patent Laid-Open No. 1 1 1 1 16679
  • Patent Literature 4 W ⁇ 97Z05191 pamphlet
  • Patent Document 5 WO 97/1 1099 pamphlet
  • Patent Document 6 Japanese Unexamined Patent Publication No. 2000-80166
  • Patent Document 7 Japanese Patent Application Laid-Open No. 2002-1 10174
  • Patent Document 8 Japanese Unexamined Patent Application Publication No. 2002-146018
  • Patent Document 9 WO 2002/081547 Pamphlet
  • Patent Document 10 W 0 2002 088219 pamphlet
  • Patent Document 1 W H 2004Z024796 Pamphlet
  • Non-Patent Document 1 Polymer Papers V o 1. 59, No. 8, 460-473 pages
  • Non-Patent Document 2 Jo rn a l o f P o y y me r S c i en c e: P a r t A: P o 1 yme r Chemi st r y, Vo l. 34, 2421-2438 (1996) Disclosure of the Invention
  • An object of the present invention is to provide a solid polymer electrolyte excellent in ionic conductivity and oxidation resistance, a solid polymer electrolyte composition comprising the solid polymer electrolyte and a polymer having ion conductivity, and any of these It is intended to provide a solid polymer electrolyte membrane, a membrane / electrode assembly using the solid polymer electrolyte membrane, and a fuel cell using the membrane electrode assembly. Means to determine the issue
  • At least one repeating unit selected from the group consisting of repeating units represented by
  • a r 1 is p-phenylene, m 1-phenylene, 2, 6-naphthylene range 4, 4, 4, 1-biphenylene, 4, 4 'One or more groups selected from monosulfonyldiphenylene, wherein Ar 2 in the above formula (III) is p-phenylene, m-phenylene, 3, 4, mono-oxydiphenylene, 4, 4 '—Oxidiphenylene, 4, 4' — Biphenylene, 4, 4 'One or more groups selected from monosulfonyldiphenylene.
  • a solid polymer electrolyte comprising 0.1 to 100 parts by mass of at least one acid selected from the group consisting of polyphosphoric acid, sulfuric acid, and methanesulfonic acid.
  • a solid polymer electrolyte membrane obtained by forming the solid polymer electrolyte according to 1 above into a film form having a thickness of 10 to 200 m.
  • a solid polymer electrolyte composition comprising the solid polymer electrolyte described in 1 above and a polymer having ion conductivity.
  • a membrane / electrode assembly wherein catalyst electrodes are provided on both surfaces of the solid polymer electrolyte membrane according to 2 or 5 above.
  • a fuel cell comprising the above-described 6-Z electrode assembly.
  • a solid polymer electrolyte or a composition thereof can be obtained, and a fuel cell using the polymer electrolyte or a composition thereof can be obtained.
  • the rigid heterocyclic polymer used in the present invention is:
  • At least one repeating unit selected from the group consisting of repeating units represented by
  • a r 1 is p-phenylene, m-phenylene, 2, 6-naphthenyl, 4, 4'-biphenylene, 4, 4 'One or more groups selected from monosulfonyldiphenylene
  • Ar 2 is p-phenylene, m-phenylene, 3, 4, mono-oxydiphenylene, 4, One or more groups selected from 4, oxydiphenylene, 4,4, bibiylene, 4,4′-monosulfonyldiphenylene.
  • the copolymer molar ratio (I I I) ((I) + (I I)) is more preferably 0 or more and 1 or less, and further preferably 0 or more and 0.5 or less.
  • the solid polymer electrolyte of the present invention comprises 100 parts by mass of an upper rigid heterocyclic polymer and at least one acid selected from the group consisting of phosphoric acid, polyphosphoric acid, sulfuric acid, and methanesulfonic acid. It consists of ⁇ 100 parts by mass.
  • the acid is present in the molded body to improve conductivity, and the acid content in the solid polymer electrolyte is preferably 0.5 to 50 mass with respect to 100 mass parts of the rigid heterocyclic polymer. Part, more preferably 1.0 to 30 parts by weight, still more preferably 3.0 to 20 parts by weight.
  • the rigid heterocyclic polymer consisting of at least one repeating unit selected from the group consisting of the repeating units represented by the formulas (I) and (I I) is represented by the following formula (A).
  • Ar 1 in the formula (A) is derived from p-phenylene, m-phenylene, 2, 6-naphthalene, 4, 4'-biphenylene, 4, 4'-sulfonyldiphenylene.
  • One or more selected groups X in formula (A) is OH, halogen atom, or
  • R is a group represented by OR, and R represents a monovalent aromatic group having 6 to 20 carbon atoms.
  • a r 2 is p-phenylene, m-phenylene, 3, 4, 1-oxydiphenylene, 4, 4'-oxydiphenylene, 4 , 4 '— Biphenylene, 4, 4' One or more groups selected from monosulfonyldiphenylene.
  • the aromatic dicarboxylic acid compound represented by the formula (A) has an aromatic ring, that is, Ar 1 force p-phenylene, m-phenylene, 2, 6-naphthylene in the formula (A).
  • Ar 1 force p-phenylene, m-phenylene, 2, 6-naphthylene in the formula (A).
  • various dicarboxylic acids other than the above formula (A) such as adipic acids can be copolymerized for the purpose of improving the properties of the polymer obtained.
  • the aromatic diamine compound represented by the formula (D) has an aromatic ring, that is, Ar 2 force p-phenylene, m-phenylene, 3, 4, monooxydiene diylene in the formula (D). , 4, 4′—oxydiphenylene, 4,4′-piphenylene, and 4,4 ′ monosulfonyldiphenylene, among which p-phenylene Len, m—Phenylene, and 3, 4 '— Oxydiff Enylene is preferred, and p-phenylene is particularly preferred.
  • various diamines other than the above formula (A) such as 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2 , 6-Diaminonaphthalene, 2, 7-Diaminonaphthalene, 2,5-Diaminopyridine, 2,6-Diaminopyridine, 3,5-Diaminopyridine, 3,3'-Diaminobiphenyl, 3,3 ' Ndidine, 3, 3'-diaminodiphenyl ether, etc. can also be copolymerized.
  • 1,4-diaminonaphthalene 1,5-diaminonaphthalene
  • 1,8-diaminonaphthalene 1,8-diaminonaphthalene
  • 2 6-Diaminonaphthalene
  • 2, 7-Diaminonaphthalene 2,5-Diaminopyridine
  • 2,6-Diaminopyridine 3,5-Diaminopyridine
  • a compound having both an amino group and a carboxyl group in the molecule for example, aminobenzoic acid can be copolymerized.
  • the solvent used for the polymerization is not particularly limited, but dissolves the raw material monomers (A), (B), (C), and (D) as described above and is substantially non-reactive with them. Any solvent can be used as long as it can obtain a polymer having a specific viscosity of at least 1.0 or more, more preferably 1.2 or more.
  • N, N, N ', N'-tetramethylurea TMU
  • N, N-dimethylacetamide DMAC
  • N, N-jetylacetamide DEAC
  • N, N-dimethylpropionamide DMPR
  • N, N-dimethylbutyramide NMBA
  • N, N-dimethylisobutyramide N-methyl-2-pyrrolidinone
  • NMP N-cyclohexyl_2monopyrrolidinone
  • NCP N-Ethylpyrrolidone I 2
  • N-Acetylpyrrolidine N-Acetylpyrrolidine (NARP), N_Acetylbiperidine
  • N— Amides such as methylpiperidone 1 (NMPD), N, N'-dimethylethyleneurea, N, N'-dimethylpropyleneurea, N, N, N ', N'
  • the preferred solvent is N, N-dimethylacetamide (DMAC) N-methyl-2-pyrrolidinone (NM P).
  • an appropriate amount of a known organic salt may be added before, during, or at the end of polymerization in order to increase solubility.
  • examples of such inorganic salts include lithium chloride and calcium chloride.
  • the polymer is produced in the same manner as a conventional polyamide solution polymerization method in the above-mentioned solvent in which the monomers (A), (B), (C), and (D) are dehydrated.
  • the reaction temperature is 80 ° or lower, preferably 60 ° or lower.
  • the concentration at this time is preferably about 1 to 2 O wt% as the monomer concentration.
  • trialkylsilyl chloride can be used for the purpose of increasing the degree of polymerization of the polymer.
  • an aliphatic or aromatic ammine or a quaternary ammonium salt can be used in combination to capture an acid such as hydrogen chloride.
  • the total amount of diamines represented by (B), (C) and (D) in the organic solvent is the aromatics represented by (A)
  • the ratio with respect to the number of moles of the dicarboxylic acid compound is preferably 0.90 to 1.10, and more preferably 0.95 to 1.05 to make a wholly aromatic polyamide.
  • the end-capping agents include benzoyl alkyd, phthalic anhydride and its substitution, hexahydrofuranic anhydride and its substitution, succinic anhydride and Examples of the substitution product and amine component include, but are not limited to, aniline and its substitution product.
  • the solid polymer electrolyte of the present invention comprises a rigid heterocyclic polymer and at least one acid selected from the group consisting of phosphoric acid, polyphosphoric acid, sulfuric acid, and methanesulfonic acid.
  • a method for adding the acids to the rigid heterocyclic polymer any method of adding to the dope in advance, adding at the time of solidification, adding after washing with water, or adding after washing with water and drying can be used. (Solid polymer electrolyte membrane and film forming method thereof)
  • the solid polymer electrolyte of the present invention is preferably in the form of a film having a thickness of 10 to 200 m.
  • a film forming method it is preferable to carry out by (i) casting method or (ii) press method.
  • the thickness of the electrolyte membrane is more preferably 30 to 100 / m.
  • a thickness of more than 10 m is preferable to obtain a membrane strength that can withstand practical use, and a thickness of less than 200 m is preferable to reduce membrane resistance, that is, to improve power generation performance.
  • the casting method it can be controlled by the solution concentration or the coating thickness on the substrate.
  • the pressing method it can be controlled by the solution concentration or the pressure of the press.
  • the casting method is a method of forming a film by casting a polymer solution (dope) containing a rigid heterocyclic polymer and a solvent on a substrate such as a glass plate and removing the solvent.
  • the solvent is not particularly limited as long as it can dissolve and remove the rigid heterocyclic polymer, and N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, N— Aprotic polar solvents such as methyl_2-pyrrolidone and hexamethylphosphonamide, and strong acids such as polyphosphoric acid, methanesulfonic acid, sulfuric acid, and trifluoroacetic acid can be used.
  • a plurality of these solvents may be used as a mixture within a possible range.
  • a solvent obtained by adding a Lewis acid such as lithium bromide, lithium chloride, or aluminum chloride to an organic solvent may be used.
  • the concentration of the rigid heterocyclic polymer in the dope is preferably 0.1 to 8% by mass. If it is too low, the formability will deteriorate, and if it is too high, the workability will deteriorate.
  • a film having a low degree of orientation in the in-plane direction can be obtained by setting the concentration of the rigid heterocyclic polymer in the dopant within a predetermined range.
  • drying temperature 0 to 2200, preferably 2O: to 1550, and further 5 to 8: 80 can be used.
  • Rigid heterocyclic polymers have high crystallinity, and ordinary extrusion film formation does not yield an isotropic film in the in-plane direction. Therefore, an isotropic film can be obtained in the in-plane direction by sandwiching a dope containing a rigid heterocyclic polymer and a solvent between the substrates and applying pressure.
  • the solvent is the same as in the casting method.
  • the concentration of the rigid bicyclic polymer in the dope is preferably 0.1 to 30% by mass, more preferably 0.5 to 8% by mass.
  • the pressure is preferably from 0.01 to 100 Mpa, more preferably from 1 to 1 OMPa. It is preferable to heat at the time of film formation.
  • the heating temperature is preferably from 100 to 30 Ot: preferably from 130 to 2550.
  • the solid polymer electrolyte of the present invention can be formed into a pellet in addition to the above-mentioned film shape.
  • Examples of the manufacturing method in the case of pellets include a compression roll method, a pre-ketting method, and a tableting method. More specifically, granulation is preferably performed using a tablet molding machine or a compression molding machine.
  • Polymer with ion conductivity used in the present invention for example, - homopolymers of S_ ⁇ 3 H yo Una monomer having an ion exchange group, a block copolymer, random copolymer, one Examples thereof include perfluorocarbon sulfonic acid resins and polyether ether ketone sulfonic acid resins having ionic conductivity, such as those introduced by subjecting SO 3 H groups and other ion exchange groups to post-treatment.
  • the polymer having ion conductivity is a perfluorocarpone sulfonic acid resin.
  • Solid polymer electrolyte composition comprising a solid polymer electrolyte and a polymer having ion conductivity
  • the solid polymer electrolyte composition of the present invention is a solid containing the rigid heterocyclic polymer. It consists of a polymer electrolyte and a polymer having ionic conductivity. Even if the solid polymer electrolyte is made of a mixture of the solid polymer electrolyte and a polymer having ion conductivity, the layer made of a film of the solid polymer electrolyte and a polymer having ion conductivity. It may be a laminate with a layer made of a film. In the case of a mixture, it is preferably 1 to 800 parts by weight, preferably 3 to 300 parts by weight, and more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the rigid heterocyclic polymer. .
  • a layer made of a polymer having ion conductivity may be provided on one side or both sides of a layer made of a rigid heterocyclic polymer.
  • the lamination method include, but are not limited to, a known press method, hot press method, cast method, spin coating method, and laminate method.
  • the membrane Z electrode assembly of the present invention (Membrane Electrode Assembly, hereinafter abbreviated as ME A) has catalyst electrodes on both surfaces of the electrolyte membrane of the present invention.
  • the catalyst electrode is one in which fine particles of catalyst metal are supported on a conductive material.
  • the catalyst metal may be any metal that promotes the oxidation reaction of hydrogen and the reduction reaction of oxygen. For example, platinum, gold, 'silver, palladium.
  • the particle size of the catalytic metal is usually 10 to 300 angstroms (l to 30 nm).
  • the conductive material may be an electron conductive material.
  • conductive materials include various metals and carbon materials.
  • the carbon material include furnace black, channel black, carbon black such as acetylene black, activated carbon, graphite and the like. These may be used alone or in combination.
  • the supported amount of catalyst metal is preferably 0.01 to: I Omg no cm 2 in the state where the electrode is formed.
  • the catalytic metal is reduced by a reduction method.
  • a method of depositing on the surface of a conductive material a method of suspending a catalyst metal in a solvent and applying this to the surface of the conductive material.
  • the solid polymer electrolyte of the present invention is preferably used for a fuel cell.
  • the fuel cell of the present invention has a single cell in which a grooved current collector for forming a fuel channel or an oxidant channel called a separator channel is arranged on the outside of the membrane electrode assembly. It is configured by laminating a plurality via a cooling plate.
  • a single cell is formed by arranging a fuel flow channel called a separator or a grooved current collector that forms an oxidant flow channel on the outside of the membrane Z electrode assembly. It is configured by laminating a plurality via a cooling plate. It is desirable to operate the fuel cell at a high temperature because the catalytic activity of the electrode increases and the electrode overvoltage decreases. However, the electrolyte membrane does not function without moisture, so it must be operated at a temperature that allows moisture management. . The preferred range of operating temperature of the fuel cell is from room temperature to 100.
  • I a value determined by the following equation based on the measured relative viscosity (re l) at 30 at a polymer concentration 0. 5 GZD 1 using concentrated sulfuric acid.
  • the electrolyte membrane of the present invention was measured for impedance in the thickness direction of the membrane at a frequency of 0.1 Hz to 65 kHz using an electrochemical impedance measuring device (Solartron, SI 1 2 8 7), and the ionic conductivity was measured. In the above measurement, electrolysis The membrane was stored at 75 in a steam atmosphere.
  • the electrolyte membrane of the present invention was soaked in Fenton reagent (containing 40 ppm of iron) heated at 60, consisting of adding 1.9 mg of iron sulfate heptahydrate to 20 ml of 30% hydrogen peroxide solution, The time required for the electrolyte membrane to dissolve in the Fenton reagent was determined.
  • the polymer dope obtained in Reference Example 1 was spread on a glass with a doctor knife, solidified in 85% phosphoric acid for 24 hours, washed with water for 1 hour, and then dried at 120 to form a membrane. A 200 / m thick electrolyte membrane was created. The phosphorus atom content was 5% by mass, and the phosphoric acid content was 15.8% by mass. The resulting cast film was measured for ionic conductivity and oxidation resistance. The results are shown in Table 1.
  • Example 2 (Creation of laminate)
  • Example 2 The film obtained in Example 1 was sandwiched between Nafion (registered trademark) films manufactured by Du Pont, Inc. having a film thickness of 170; am, and the ionic conductivity and oxidation resistance were measured. The results are shown in Table 1.
  • Reference Example 2 Polymer polymerization
  • the polymer dope obtained in Reference Example 2 was spread on a glass with a doctor knife, solidified in 85% phosphoric acid for 24 hours, washed with water for 1 hour, and dried at 120 to form a film.
  • An electrolyte membrane with a thickness of 40; am was prepared.
  • the phosphorus atom content was 6% by mass, and the phosphoric acid content was about 19% by mass.
  • Table 1 shows the measurement results of the physical properties of the obtained cast film.
  • Example 4 (Creation of laminate)
  • Example 5 Preparation of membrane electrode assembly (MEA) Using the cast film (electrolyte membrane) obtained in Example 3, a laminate composed of a catalyst electrode Z electrolyte membrane / catalyst electrode was prepared by a hot press method.
  • MEA membrane electrode assembly
  • Ones catalyst-electrodes are composed of a catalyst layer composed of carbon emissions carrier carrying platinum of 1 mg / cm 2 of basis weight which is an electrode substrate and a supported catalyst comprising a carbon paper Teflon-treated product of the thickness of 400 // m Was used.
  • Hot press conditions were a pressure of 100 kg Kcm 2 (9.8 Pa), a temperature of 150 ° C, and a holding time of 3 minutes.
  • Table 2 shows a list of output characteristics at each temperature. table 1 Table 2

Abstract

L'invention concerne un électrolyte polymère qui comporte 100 parties en masse d'un polymère hétérocyclique rigide et de 0,1 à 100 parties en masse d'au moins un acide sélectionné dans le groupe constitué par l'acide phosphorique, l'acide polyphosphorique, l'acide sulfurique et l'acide méthanesulfonique, le polymère hétérocyclique rigide comportant principalement au moins une unité se répétant sélectionnée dans le groupe constitué par les unités se répétant représentées par les formules (I) et (II), et une unité se répétant représentée par la formule (III), et le rapport de copolymérisation sur une base molaire entre les unités se répétant (I), (II) et (III) (c'est-à-dire rapport (III)/((I + (II)) étant dans la plage de 0 à 5 (y compris), la viscosité inhérente étant de 0,05 à 100 dl/g lorsque mesurée dans une solution d'acide sulfurique à une concentration de 0,5 g/100 ml à 25°C; une composition d'électrolyte polymère solide comportant l'électrolyte polymère solide et un polymère ayant une conductivité ionique; une membrane d'électrolyte polymère solide comportant l'électrolyte polymère solide ou la composition d'électrolyte polymère solide; un ensemble membrane/électrode utilisant la membrane d'électrolyte polymère solide; et une pile à combustible utilisant l'ensemble membrane/électrolyte (I), (II) et (III).
PCT/JP2008/053713 2007-02-27 2008-02-25 Électrolyte polymère solide WO2008105547A1 (fr)

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WO2013019581A1 (fr) * 2011-07-29 2013-02-07 E. I. Du Pont De Nemours And Company Procédé de fabrication d'un copolymère d'aramide
US8716433B2 (en) 2011-07-29 2014-05-06 E I Du Pont De Nemours And Company Aramid copolymer
US8716434B2 (en) 2011-07-29 2014-05-06 E I Du Pont De Nemours And Company Aramid copolymer
US8716431B2 (en) 2011-07-29 2014-05-06 E I Du Pont De Nemours And Company Process for preparing aramid copolymer
US8716432B2 (en) 2011-07-29 2014-05-06 E I Du Pont De Nemours And Company Process for forming an aramid copolymer
US8809434B2 (en) 2011-07-29 2014-08-19 Ei Du Pont De Nemours And Company Process for preparing aramid copolymer
US8822632B2 (en) 2011-07-29 2014-09-02 E I Du Pont De Nemours And Company Process for forming an aramid copolymer
US8907051B2 (en) 2011-07-29 2014-12-09 E I Du Pont De Nemours And Company Process for forming an aramid copolymer
US8907052B2 (en) 2011-07-29 2014-12-09 E I Du Pont De Nemours And Company Process of forming an aramid copolymer
US9732442B2 (en) 2012-01-11 2017-08-15 E I Du Pont De Nemours And Company Process for preparing aramid copolymer yarn having low residual sulfur
US9845553B2 (en) 2012-01-11 2017-12-19 E I Du Pont De Nemours And Company Process for preparing aramid copolymer yarn using an acid wash
US10240282B2 (en) 2012-01-11 2019-03-26 E I Du Pont De Nemours And Company Process for preparing aramid copolymer yarn using a halide acid wash

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Publication number Priority date Publication date Assignee Title
WO2013019581A1 (fr) * 2011-07-29 2013-02-07 E. I. Du Pont De Nemours And Company Procédé de fabrication d'un copolymère d'aramide
US8716433B2 (en) 2011-07-29 2014-05-06 E I Du Pont De Nemours And Company Aramid copolymer
US8716434B2 (en) 2011-07-29 2014-05-06 E I Du Pont De Nemours And Company Aramid copolymer
US8716431B2 (en) 2011-07-29 2014-05-06 E I Du Pont De Nemours And Company Process for preparing aramid copolymer
US8716432B2 (en) 2011-07-29 2014-05-06 E I Du Pont De Nemours And Company Process for forming an aramid copolymer
US8716430B2 (en) 2011-07-29 2014-05-06 E I Du Pont De Nemours And Company Aramid copolymer
CN103857728A (zh) * 2011-07-29 2014-06-11 纳幕尔杜邦公司 形成芳族聚酰胺共聚物的方法
US8809434B2 (en) 2011-07-29 2014-08-19 Ei Du Pont De Nemours And Company Process for preparing aramid copolymer
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JP2014521788A (ja) * 2011-07-29 2014-08-28 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー アラミド共重合体
US8822632B2 (en) 2011-07-29 2014-09-02 E I Du Pont De Nemours And Company Process for forming an aramid copolymer
US8835600B2 (en) 2011-07-29 2014-09-16 E I Du Pont De Nemours And Company Process of forming an aramid copolymer
US8907051B2 (en) 2011-07-29 2014-12-09 E I Du Pont De Nemours And Company Process for forming an aramid copolymer
US8907052B2 (en) 2011-07-29 2014-12-09 E I Du Pont De Nemours And Company Process of forming an aramid copolymer
US8921512B2 (en) 2011-07-29 2014-12-30 E I Du Pont De Nemours And Company Process for forming an aramid copolymer
US9115244B2 (en) 2011-07-29 2015-08-25 E I Du Pont De Nemours And Company Process for forming an aramid copolymer
US9127143B2 (en) 2011-07-29 2015-09-08 E I Du Pont De Nemours And Company Aramid copolymer
CN103857728B (zh) * 2011-07-29 2016-03-16 纳幕尔杜邦公司 形成芳族聚酰胺共聚物的方法
US9732442B2 (en) 2012-01-11 2017-08-15 E I Du Pont De Nemours And Company Process for preparing aramid copolymer yarn having low residual sulfur
US9845553B2 (en) 2012-01-11 2017-12-19 E I Du Pont De Nemours And Company Process for preparing aramid copolymer yarn using an acid wash
US10240282B2 (en) 2012-01-11 2019-03-26 E I Du Pont De Nemours And Company Process for preparing aramid copolymer yarn using a halide acid wash

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