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WO2018151254A1 - Composition liquide, membrane électrolytique polymère solide et ensemble membrane-électrode - Google Patents

Composition liquide, membrane électrolytique polymère solide et ensemble membrane-électrode Download PDF

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Publication number
WO2018151254A1
WO2018151254A1 PCT/JP2018/005497 JP2018005497W WO2018151254A1 WO 2018151254 A1 WO2018151254 A1 WO 2018151254A1 JP 2018005497 W JP2018005497 W JP 2018005497W WO 2018151254 A1 WO2018151254 A1 WO 2018151254A1
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Prior art keywords
group
compound
polymer electrolyte
solid polymer
electrolyte membrane
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PCT/JP2018/005497
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English (en)
Japanese (ja)
Inventor
英夫 澤田
祐梨 及川
淳 渡壁
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Hirosaki University NUC
AGC Inc
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Asahi Glass Co Ltd
Hirosaki University NUC
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Priority to JP2018568627A priority Critical patent/JPWO2018151254A1/ja
Publication of WO2018151254A1 publication Critical patent/WO2018151254A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/10—Homopolymers or copolymers of unsaturated ethers
    • 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
    • H01M8/1037—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes
    • 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 liquid composition, a solid polymer electrolyte membrane, a membrane electrode assembly, a solid polymer fuel cell, and methods for producing them.
  • the polymer electrolyte fuel cell has a structure in which, for example, a cell is formed by sandwiching a membrane electrode assembly between two separators, and a plurality of cells are stacked.
  • the membrane / electrode assembly includes an anode and a cathode having a catalyst layer, and a solid polymer electrolyte membrane disposed between the anode and the cathode.
  • the reaction at each electrode of the polymer electrolyte fuel cell is expressed by the following equation when the fuel is hydrogen gas.
  • the thickness of the polymer electrolyte membrane from the viewpoint of improving the power generation performance of the fuel cell by reducing the resistance of the polymer electrolyte membrane.
  • the fuel hydrogen gas, methanol, etc.
  • the fuel supplied to the anode side permeates (cross leaks) the solid polymer electrolyte membrane and easily moves to the cathode side.
  • the fuel cross-leaks the fuel that does not contribute to the electrochemical reaction in the fuel cell increases, resulting in a decrease in fuel efficiency.
  • Non-Patent Documents 1 and 2 As a solid polymer electrolyte membrane in which cross-leakage of fuel is suppressed, a solid polymer electrolyte membrane containing an inorganic layered compound (montmorillonite or the like) has been proposed (Non-Patent Documents 1 and 2).
  • Non-Patent Document 1 When the solid polymer electrolyte membrane described in Non-Patent Document 1 is produced, Na + of montmorillonite is substituted with protons, and the fluorine-containing electrolyte polymer and proton-type montmorillonite are further dispersed in water by ultrasonic treatment, and 180 A film is formed by supplying dry nitrogen in a chamber at a high temperature and a high pressure of 1.24 MPa. Therefore, a solid polymer electrolyte membrane cannot be easily manufactured.
  • the fluorine-containing electrolyte polymer and montmorillonite are dispersed in a high boiling point solvent by ultrasonic treatment. Moreover, when forming a solid polymer electrolyte membrane, in order to remove a high boiling point solvent, after drying at high temperature, it is washed with water. Therefore, a solid polymer electrolyte membrane cannot be easily manufactured.
  • the present invention relates to a liquid composition capable of easily producing a solid polymer electrolyte membrane in which cross-leakage of fuel is suppressed, and a method for producing the same; a solid polymer electrolyte membrane in which cross-leakage of fuel is suppressed and which can be easily produced;
  • Production method Provided are a membrane electrode assembly and a polymer electrolyte fuel cell provided with a solid polymer electrolyte membrane that can suppress the cross-leakage of fuel and can be easily produced, and a production method thereof.
  • the present invention has the following aspects. ⁇ 1> a fluorine-containing electrolyte polymer; Hydrolyzable silyl group-containing compound represented by the following formula (I), hydrolyzate of the silyl group-containing compound, condensate of the silyl group-containing compound, hydrolyzable silyl group represented by the following formula (II) -Containing compound, hydrolyzate of the silyl group-containing compound, and condensate of the silyl group-containing compound, a hydrolyzable silyl group-containing compound represented by the following formula (I) and a hydrolyzate represented by the following formula (II)
  • a liquid composition comprising at least one silane compound selected from the group consisting of condensates of degradable silyl group-containing compounds, an inorganic layered compound, and a liquid medium.
  • R f is a monovalent organic group having a fluorine atom
  • R 1 is a hydrogen atom or an alkyl group
  • Q is a single bond or an alkylene group when p is 0, and p is 1.
  • L is a hydrolyzable group
  • R 2 is a hydrogen atom or a monovalent hydrocarbon group
  • p is 0 or 1
  • m is 1 to 3
  • n is 1 ⁇ 6)
  • R f , L, R 2 and m are the same as defined in formula (I), but each is independent and may be the same as or different from that in formula (I).
  • k is 1 to 3.
  • the content of the inorganic layered compound is 0.2 to 20% by mass based on the total of the fluorine-containing electrolyte polymer, the inorganic layered compound, and the silane compound, ⁇ 1> or ⁇ 2> Liquid composition.
  • the content of the silane compound is 0.1 to 10% by mass with respect to the total of the fluorine-containing electrolyte polymer, the inorganic layered compound, and the silane compound, and any one of ⁇ 1> to ⁇ 3>
  • a fluorine electrolyte polymer Hydrolyzable silyl group-containing compound represented by the following formula (I), hydrolyzate of the compound, condensate of the compound, hydrolyzable silyl group-containing compound represented by the following formula (II), Hydrolyzate and condensate of the compound, from the group consisting of a hydrolyzable silyl group-containing compound represented by the following formula (I) and a condensate of the hydrolyzable silyl group-containing compound represented by the following formula (II) At least one silane compound selected; An inorganic stratiform compound or a reaction product of the inorganic stratiform compound and the silane compound; A solid polymer electrolyte membrane.
  • R f is a monovalent organic group having a fluorine atom
  • R 1 is a hydrogen atom or an alkyl group
  • Q is a single bond or an alkylene group when p is 0, and p is When it is 1, it is an alkylene group
  • L is a hydrolyzable group
  • R 2 is a hydrogen atom or a monovalent hydrocarbon group
  • p is 0 or 1
  • m is an integer of 1 to 3.
  • the total content of the silane compound, the inorganic layered compound, and the reaction product of the silane compound and the inorganic layered compound is 0.3 to 30% by mass with respect to the solid polymer electrolyte membrane ⁇ 7> or ⁇ 8>
  • the solid polymer electrolyte membrane ⁇ 10> The solid polymer electrolyte membrane according to any one of ⁇ 7> to ⁇ 9>, wherein the solid polymer electrolyte membrane has a thickness of 1 to 25 ⁇ m.
  • ⁇ 11> an anode having a catalyst layer, a cathode having a catalyst layer, and the solid polymer electrolyte membrane according to any one of ⁇ 7> to ⁇ 10> disposed between the anode and the cathode;
  • a membrane electrode assembly comprising: ⁇ 12>
  • a polymer electrolyte fuel cell comprising the membrane electrode assembly according to ⁇ 11>.
  • the inorganic layered compound, the hydrolyzable silyl group-containing compound represented by the formula (I) and / or the formula (II), and the liquid medium are mixed to obtain a liquid mixture.
  • the method for producing a liquid composition according to ⁇ 13> wherein the liquid mixture and the fluorine-containing electrolyte polymer are mixed.
  • a solid polymer electrolyte membrane wherein a liquid composition is prepared by the method for producing a liquid composition according to ⁇ 13> or ⁇ 14>, and a solid polymer electrolyte membrane is formed using the obtained liquid composition Production method.
  • ⁇ 17> The method for producing a solid polymer electrolyte membrane according to ⁇ 15> or ⁇ 16>, wherein the solid polymer electrolyte membrane is formed and then heat-treated at 110 to 220 ° C.
  • a method for producing a membrane electrode assembly comprising an anode having a catalyst layer, a cathode having a catalyst layer, and a solid polymer electrolyte membrane disposed between the anode and the cathode, A method for producing a membrane / electrode assembly, wherein a solid polymer electrolyte membrane is produced by any one of the methods ⁇ 15> to ⁇ 17>.
  • a method for producing a polymer electrolyte fuel cell comprising a membrane electrode assembly, wherein the membrane electrode assembly is produced by the method for producing a membrane electrode assembly according to ⁇ 18>. Battery manufacturing method.
  • a solid polymer electrolyte membrane in which cross-leakage of fuel is suppressed can be easily produced.
  • the solid polymer electrolyte membrane of the present invention can be easily manufactured with reduced fuel cross-leakage.
  • the membrane electrode assembly of the present invention includes a solid polymer electrolyte membrane that can suppress cross-leakage of fuel and can be easily manufactured.
  • the solid polymer fuel cell of the present invention includes a solid polymer electrolyte membrane that can suppress cross-leakage of fuel and can be easily manufactured.
  • FIG. 1 is a scanning electron micrograph of a cross section of the solid polymer electrolyte membrane of Example 1.
  • FIG. 3 is a scanning electron micrograph of a cross section of the solid polymer electrolyte membrane of Example 2.
  • FIG. 4 is a scanning electron micrograph of a cross section of the solid polymer electrolyte membrane of Example 3.
  • FIG. 6 is a scanning electron micrograph of the cross section of the solid polymer electrolyte membrane of Example 6.
  • a unit represented by the formula (u1) is referred to as a unit (u1). Units represented by other formulas will be described accordingly.
  • a compound represented by the formula (m1) will be referred to as a compound (m1). The compounds represented by other formulas will be described accordingly.
  • the “inorganic layered compound” means a layered inorganic compound having cations that can be easily ion-exchanged with other cations on the crystal surface between crystal layers.
  • the “fluorinated electrolyte polymer” means a polymer having a fluorine atom and an ion exchange group.
  • the “ion exchange group” means a group that can exchange a part of the cation contained in the group with another cation. Examples of the ion exchange group include a group having H + , a monovalent metal cation, an ammonium ion, and the like.
  • the “hydrolyzable silyl group” means a group that can form a silanol group (Si—OH) by a hydrolysis reaction.
  • “Unit” means a polymerized unit derived from a monomer formed by polymerization of the monomer.
  • the unit may be a unit directly formed by a polymerization reaction of a monomer, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
  • the “etheric oxygen atom” means an oxygen atom that forms an ether bond between carbon-carbon atoms.
  • “Fuel” refers to a substance that serves as a fuel in a polymer electrolyte fuel cell, such as hydrogen gas in a polymer electrolyte fuel cell, methanol in a direct methanol fuel cell, or the like.
  • the “fuel” in the present invention is hydrogen gas or methanol unless otherwise specified.
  • the liquid composition of the present invention comprises: a fluorine-containing electrolyte polymer; an inorganic layered compound; a specific hydrolyzable silyl group-containing compound, a hydrolyzate of the hydrolyzable silyl group-containing compound, and the hydrolyzable silyl group-containing compound And at least one silane compound selected from the group consisting of these condensates (hereinafter also referred to as “specific silane compound”); and a liquid medium.
  • the liquid composition of the present invention may contain components other than essential components as necessary.
  • the fluorine-containing electrolyte polymer has an ion exchange group.
  • the ion exchange group include an acid type in which the cation is a proton, and a salt type in which the cation is a metal ion, an ammonium ion, or the like.
  • a fluorine-containing electrolyte polymer having an acid type ion exchange group is usually used.
  • a part of protons of the ion exchange group may be ion-exchanged with cerium ion, manganese ion or the like.
  • Examples of the acid-type ion exchange group include a sulfonic acid group, a sulfonimide group, a sulfonemethide group, a phosphonic acid group, a carboxylic acid group, and a ketoimide group. From the viewpoint of strong acidity and high chemical stability, a sulfonic acid group, a sulfonimide group or a sulfonemethide group is preferable, a sulfonic acid group or a sulfonimide group is more preferable, and a sulfonic acid group is further preferable.
  • fluorine-containing electrolyte polymer a perfluorocarbon polymer having an ion exchange group which may contain an etheric oxygen atom is preferable from the viewpoint of durability of the solid polymer electrolyte membrane.
  • the perfluorocarbon polymer one of the following unit (u1) and unit (u2) from the viewpoint of chemical stability, proton conductivity, hot water resistance, and mechanical properties required when operating the fuel cell. Or the polymer which has both (henceforth the polymer H) is preferable.
  • the polymer H preferably further has a unit (hereinafter referred to as TFE unit) based on tetrafluoroethylene (hereinafter referred to as TFE) from the viewpoint of excellent mechanical properties and chemical durability of the polymer H.
  • TFE unit tetrafluoroethylene
  • the polymer H may further have structural units based on other monomers (hereinafter referred to as other units) other than the unit (u1), the unit (u2), and the TFE unit, as necessary.
  • Unit (u1) is expressed by the following formula.
  • Q 2 is a single bond, or an ether oxygen atom good perfluoroalkylene group which may have a
  • Y 2 is a fluorine atom or a monovalent perfluoro organic group
  • t is 0 or 1
  • R f2 is a perfluoroalkyl group which may have an etheric oxygen atom
  • X 2 is an oxygen atom, a nitrogen atom or a carbon atom
  • b is 0 when X 2 is an oxygen atom.
  • X 2 when X 2 is a nitrogen atom, 1 when X 2 is a carbon atom, Z + is H + , a monovalent metal ion, or one or more hydrogen atoms are replaced with a hydrocarbon group It may be an ammonium ion.
  • a single bond means that the carbon atom of CFY 2 and the sulfur atom of SO 2 are directly bonded.
  • An organic group means a group containing one or more carbon atoms.
  • the oxygen atom may be one or two or more.
  • the oxygen atom may be inserted between the carbon atom-carbon atom bonds of the perfluoroalkylene group or may be inserted at the carbon atom bond terminal.
  • the oxygen atom is not inserted into the carbon atom bond terminal bonded to sulfur among the carbon atom bond terminals of the perfluoroalkylene group.
  • the perfluoroalkylene group may be linear or branched.
  • the perfluoroalkylene group preferably has 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. If the number of carbon atoms is 6 or less, a decrease in the ion exchange capacity of the polymer H is suppressed, and a decrease in proton conductivity is easily suppressed.
  • the perfluoroalkyl group for R f2 may be linear or branched, and is preferably linear.
  • the perfluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the perfluoroalkyl group is preferably a perfluoromethyl group, a perfluoroethyl group, or the like.
  • Y 2 is preferably a fluorine atom or a trifluoromethyl group.
  • the unit (u1) the following units (u1-1) to (u1-4) are preferable from the viewpoint of easy production of the polymer H and easy industrial implementation.
  • Q 11 is a perfluoroalkylene group which may have an etheric oxygen atom
  • Q 12 is a perfluoroalkylene group which may have a single bond or an etheric oxygen atom
  • Y 1 Is a fluorine atom or a monovalent perfluoro organic group, s is 0 or 1
  • R f1 is a perfluoroalkyl group optionally having an etheric oxygen atom
  • X 1 is an oxygen atom
  • a nitrogen atom or a carbon atom, a is 0 when X 1 is an oxygen atom, 1 when X 1 is a nitrogen atom, 2 when X 1 is a carbon atom
  • Z + is H +
  • a single bond means that the carbon atom of CY 1 and the sulfur atom of SO 2 are directly bonded.
  • An organic group means a
  • the oxygen atom may be one or two or more.
  • the oxygen atom may be inserted between the carbon atom-carbon atom bonds of the perfluoroalkylene group or may be inserted at the carbon atom bond terminal.
  • the oxygen atom is not inserted into the carbon atom bond terminal bonded to sulfur among the carbon atom bond terminals of the perfluoroalkylene group.
  • the perfluoroalkylene group may be linear or branched, and is preferably linear.
  • the perfluoroalkylene group preferably has 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms.
  • the number of carbon atoms is 6 or less, the boiling point of the raw material monomer becomes low, and distillation purification becomes easy. Moreover, if carbon number is 6 or less, the fall of the ion exchange capacity of the polymer H will be suppressed, and the fall of proton conductivity will be suppressed.
  • Q 12 is preferably a C 1-6 perfluoroalkylene group which may have an etheric oxygen atom.
  • At least one of Q 11 and Q 12 is preferably a C 1-6 perfluoroalkylene group having an etheric oxygen atom. Since the monomer having such a fluoroalkylene group can be synthesized without undergoing a fluorination reaction with a fluorine gas, the yield is good and the production is easy.
  • the perfluoroalkyl group for R f1 may be linear or branched, and is preferably linear.
  • the perfluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
  • As the perfluoroalkyl group a perfluoromethyl group, a perfluoroethyl group and the like are preferable.
  • R f1 may be the same group or different groups.
  • Y 1 is preferably a fluorine atom or a linear perfluoroalkyl group having 1 to 6 carbon atoms which may have an etheric oxygen atom.
  • the units (u2) are preferably units (u2-1) to (u2-3) from the viewpoint of easy production of the polymer H and easy industrial implementation.
  • the unit (u2-2) or the unit (u2- 3) is more preferable.
  • the other unit is a unit based on another monomer other than the unit (u1), the unit (u2) and the TFE unit.
  • Other monomers include, for example, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, ethylene, propylene, perfluoro ⁇ -olefin (hexafluoropropylene, etc.), (perfluoroalkyl) ethylene ((perfluorobutyl) Ethylene, etc.), (perfluoroalkyl) propene (3-perfluorooctyl-1-propene, etc.), perfluorovinyl ether (perfluoro (alkyl vinyl ether)), perfluoro (etheric oxygen atom-containing alkyl vinyl ether), etc.), International Publication No.
  • the polymer H may have one each of the unit (u1), the unit (u2), and other units, or may have two or more of each.
  • the proportion of each unit in the polymer H may be appropriately adjusted according to the ion exchange capacity, proton conductivity, hydrogen gas permeability, hot water resistance, mechanical properties, etc. required for the electrolyte polymer.
  • the ion exchange capacity of the electrolyte polymer is preferably 0.7 to 2.5 meq / g dry resin, more preferably 0.9 to 2.2 meq / g dry resin. If it is more than the lower limit of the said range, proton conductivity will become high easily and sufficient battery output will be easy to be obtained. If the amount is not more than the upper limit of the above range, the synthesis of a polymer having a high molecular weight is easy, and the electrolyte polymer is not easily swollen with water, so that the mechanical strength is easily maintained.
  • the polymer H is produced by converting the —SO 2 F group of the precursor polymer F to an ion exchange group. That is, the polymer F has a structure in which the —SO 2 X 2 (SO 2 R f2 ) b — Z + group in the unit (u1) of the polymer H is substituted with the —SO 2 F group, and the unit (u2) of the polymer H And —SO 2 X 1 (SO 2 R f1 ) a — Z + group has one or both of structures in which —SO 2 F group is substituted.
  • the polymer F is produced by polymerizing one or both of the compound (m1) and the compound (m2), and if necessary, TFE and other monomers.
  • the compound (m1) is represented by the following formula.
  • Q 2, Y 2, t is the same as Q 2, Y 2, t in the unit (u1), a preferred form same.
  • Compound (m1) is, for example, D.I. J. et al. Vauham, “Du Pont Innovation”, Vol. 43, No. 3, 1973, p. 10 and the method described in the examples of US Pat. No. 4,358,412 can be used for the production by known synthetic methods.
  • the compound (m2) is represented by the following formula.
  • Q 11, Q 12, Y 1 , s is the same as Q 11, Q 12, Y 1 , s in the unit (u2), which is the preferred form as well.
  • Compound (m2) can be produced by a known synthesis method such as the method described in International Publication No. 2007/013533.
  • the polymerization method for producing the polymer (F) is not particularly limited, and includes conventionally known methods.
  • Examples of the method for converting the —SO 2 F group of the polymer F into an ion exchange group include the method described in International Publication No. 2011/013578.
  • the -SO 2 F groups acid form sulfonic acid groups - as a method of converting the (-SO 3 H + groups), salt was hydrolyzed -SO 2 F groups of the polymer F into contact with the base
  • a method of converting the salt-type sulfonic acid group into an acid-type sulfonic acid group by bringing the salt-type sulfonic acid group into contact with an acid to form an acid form.
  • Inorganic layered compound examples of the cation that can be easily ion-exchanged with other cations existing on the crystal surface between the crystal layers of the inorganic layered compound include metal ions such as sodium and calcium, and organic cations such as quaternary ammonium. These cations are easily ion-exchanged with other cations, and various substances having a cationic property are inserted between the crystal layers of the inorganic layered substance.
  • inorganic layered compounds examples include smectite, kaolinite, sericite, glowconite, chlorite, talc, vermiculite, halloysite, swellable mica, ⁇ -form crystalline zirconium phosphate, ⁇ -form crystalline zirconium phosphate, etc. Can be mentioned.
  • examples of the smectite include montmorillonite, saponite, hectorite, beidellite, stevensite, and nontronite. Montmorillonite is preferable from the viewpoint of dispersibility and film formability.
  • the inorganic layered compound may be a natural product or a synthetic product, and may be used alone or in combination of two or more.
  • the specific silane compound (also referred to as silane compound X) in the present invention is a silane compound represented by the following formula (I) (hereinafter also referred to as compound I), a hydrolyzate of compound I, a condensate of compound I, A hydrolyzable silyl group-containing compound represented by the following formula (II) (hereinafter also referred to as compound II), a hydrolyzate of compound II, and a condensate of compound II, a hydrolyzate represented by the following formula (I) It is at least one selected from the group consisting of a condensate of a decomposable silyl group-containing compound and a hydrolyzable silyl group-containing compound represented by the following formula (II).
  • R f is a monovalent organic group having a fluorine atom
  • R 1 is hydrogen atom or an alkyl group
  • Q is, when p is 0 is a single bond or an alkylene group, p is 1 Is an alkylene group, L is a hydrolyzable group
  • R 2 is a hydrogen atom or a monovalent hydrocarbon group, p is 0 or 1, and m is an integer of 1 to 3.
  • N is 1-6.
  • R f , L, R 2 , and m are the same as defined in the formula (I), but are independent of the formula (I), and each content is the same as that of the formula (I). They may be the same or different.
  • k is 1 to 3.
  • Condensates may be formed by intramolecular or intermolecular condensation reactions.
  • the condensate of Compound I and Compound II includes a product of an intramolecular or intermolecular condensation reaction in Compound I, Compound II, or a hydrolyzate of Compound I or Compound II.
  • R f is preferably a polyfluoroalkyl group or a polyfluoroether group from the viewpoint of availability of raw materials.
  • the group represented by the following formula (III) or the following formula ( The group represented by IV) is more preferred.
  • -(CF 2 ) q X III) —CF (CF 3 ) — (OCF 2 CF (CF 3 )) r —OC 3 F 7 (IV)
  • X is a hydrogen atom or a halogen atom
  • q is an integer of 1 to 15
  • r is an integer of 0 to 8.
  • — (CF 2 ) 3 F, — (CF 2 ) 6 F, — (CF 2 ) 2 F, — (CF 2 ) 4 are used because the raw materials are easily available. F, — (CF 2 ) 5 F and the like are preferable.
  • —CF (CF 3 ) OC 3 F 7 , —CF (CF 3 ) OCF 2 CF (CF 3 ) OC 3 F can be used because the raw material of compound I is easily available. 7 , -CF (CF 3 ) (OCF 2 CF (CF 3 )) 2 OC 3 F 7 and the like are preferable.
  • R 1 in the formula (I) when p is 0, a hydrogen atom is preferable because the raw material of the compound I is easily available.
  • R 1 when p is 1, a hydrogen atom or a methyl group is preferable from the viewpoint of easy availability of the raw material of compound I.
  • L in the formulas (I) and (II) is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, Si-L at the end of Compound I and Compound II becomes a silanol group (Si—OH) by hydrolysis reaction. Silanol groups react within or between molecules to form Si—O—Si bonds. In addition, the silanol group reacts with the inorganic layered compound to form a chemical bond (inorganic layered compound-O-Si).
  • Examples of L include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (—NCO).
  • L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of easy availability of raw materials.
  • a chlorine atom is particularly preferable.
  • L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of low outgassing during coating and excellent storage stability of compounds I and II, and when long-term storage stability of compounds I and II is required. Is more preferably an ethoxy group, and more preferably a methoxy group when the reaction time after coating is short.
  • Examples of the monovalent hydrocarbon group represented by R 2 in the formulas (I) and (II) include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group.
  • R 2 is preferably a monovalent hydrocarbon group, and more preferably a monovalent saturated hydrocarbon group.
  • the number of carbon atoms of the monovalent saturated hydrocarbon group is preferably from 1 to 6, more preferably from 1 to 3, and even more preferably from 1 to 2, from the viewpoint of easy availability of the raw material of Compound I.
  • n is preferably 2 or 3, and more preferably 2 from the viewpoint that the effects of the present invention are sufficiently exhibited.
  • M in the formulas (I) and (II) is preferably 2 or 3, more preferably 3, from the viewpoint that the effects of the present invention are sufficiently exhibited.
  • Compound I Preferred examples of Compound I are as follows. Compound I may be used alone or in combination of two or more.
  • Compound I is produced by reacting a fluoroalkanoyl peroxide represented by the following formula (V) with a silane compound represented by the following formula (VI) in a solvent (such as a halogenated aliphatic hydrocarbon). It can.
  • N in the formula (I) corresponds to the degree of polymerization of the silane compound represented by the formula (VI).
  • R f C (O) O—OC (O) R f (V) CH 2 CR 1- (C (O) O) p -Q-SiL m R 2 3-m (VI)
  • fluoroalkanoyl peroxide represented by the formula (V) the following are preferable from the viewpoint of availability of the raw materials R f COF, R f COCl or (R f CO) 2 O.
  • the silane compound represented by the formula (VI) is more preferably CH 2 ⁇ CH—Si (OCH 3 ) 3 from the viewpoint that the effects of the present invention are sufficiently exhibited.
  • the compound is then subjected to a hydrosilation reaction with HSi (OCH 3 ) 3 , HSi (OCH 2 CH 3 ) 3 or HSiCH 3 (OCH 3 ) 2 in the presence of a Pt-containing catalyst, thereby causing R f —CH 2 CH 2 —Si (OCH 3 ) 3 , R f —CH 2 CH 2 —Si (OCH 2 CH 3 ) 3 or R f —CH 2 CH 2 —SiCH 3 (OCH 3 ) 2 is synthesized.
  • R f —CH 2 CH 2 —SiCl 3 is synthesized by performing a hydrosilation reaction using HSiCl 3 , and reacted with methanol or ethanol to thereby produce R f —CH 2 CH 2 —Si (OCH 3 ) 3 or R f —CH 2 CH 2 —Si (OCH 2 CH 3 ) 3 is synthesized.
  • hydrosilation reaction is performed using HSiCH 3 Cl 2
  • R f —CH 2 CH 2 —SiCH 3 Cl 2 is obtained, and when methanol is reacted therewith, R f —CH 2 CH 2 —SiCH 3 (OCH 3 2 ) is synthesized.
  • the compounds represented by R f -I are preferably the following compounds from the viewpoint of availability of synthesis and the effects of the present invention.
  • an iodide containing an ether oxygen atom is obtained by allowing potassium carbonate and iodine to act on the following acyl fluoride by the method described in the Russian Journal of General Chemistry, 81 (9), 1829-1833, (2011). Is synthesized. CF 3 CF 2 CF 2 OCF (CF 3 ) -COF CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) -COF CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) -COF
  • R f —CH 2 CH 2 CH 2 —SiCl 3 is synthesized by carrying out a hydrosilation reaction using HSiCl 3 , and reacted with methanol or ethanol to produce R f —CH 2 CH 2 CH 2 —.
  • Si (OCH 3 ) 3 or R f —CH 2 CH 2 CH 2 —Si (OCH 2 CH 3 ) 3 is synthesized.
  • hydrosilylation reaction is performed using HSiCH 3 Cl 2
  • R f —CH 2 CH 2 CH 2 —SiCH 3 Cl 2 is obtained, and when reacted with methanol, R f —CH 2 CH 2 CH 2 —SiCH is obtained.
  • 3 (OCH 3 ) 2 is synthesized.
  • the compound represented by R f -I is preferably the same as described above from the viewpoint of availability of synthesis and the effect of the present invention.
  • the liquid medium preferably contains water or contains water and alcohol since the dispersibility of the fluorine-containing electrolyte polymer, inorganic layered compound, compound I, and compound II is good.
  • an alcohol having a branched or straight chain alkyl group having 1 to 4 carbon atoms or a branched or straight chain polyfluoroalkyl group having 1 to 4 carbon atoms is preferable.
  • methanol, ethanol, 1-propanol, 2-propanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol, 2,2,3, Examples include 3-tetrafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, and 3,3,3-trifluoro-1-propanol.
  • Alcohol may be used alone or in combination of two or more.
  • the mass ratio of water to alcohol is preferably 100/0 to 5/95, more preferably 70/30 to 30/70. If it is in the said range, the drying rate at the time of film
  • the total content of water and alcohol in the liquid medium is preferably 70% by mass or more, more preferably 75% by mass or more, and further preferably 100% by mass. Within the above range, the dispersibility of the inorganic layered compound tends to be good.
  • the liquid medium may include other liquid medium other than water and alcohol.
  • Other liquid media include hydrofluorocarbons such as 1H, 4H-perfluorobutane, 1H-perfluorohexane, 1,1,1,2,3,4,4,5,5,5-decafluoropentane; -Hydrochlorofluorocarbons such as dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane; 1,1,2,2- Tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoro Methyl) pentane, ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, methyl nonafluorobuty
  • the viscosity of the liquid composition can be adjusted by adding one or more of these fluorine-containing solvents.
  • the content ratio of the other liquid medium in the liquid medium is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 0% by mass. Within the above range, it is difficult to inhibit the dispersibility of the inorganic layered compound. In the present invention, it is not necessary to add a high boiling point solvent such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol, propylene glycol, etc. Good.
  • the solid content in the liquid composition is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 5 to 20% by mass. If it is more than the lower limit of the said range, the viscosity of a liquid composition will become high easily, and when a liquid composition is apply
  • the content of the fluorine-containing electrolyte polymer is preferably 70 to 99.7% by mass, more preferably 82 to 99.3% by mass, based on the total of the fluorine-containing electrolyte polymer, the inorganic layered compound, and the silane compound X. More preferable is 98.5% by mass. If it is more than the lower limit of the said range, the fall of the proton conductivity of a solid polymer electrolyte membrane will be easy to be suppressed. If it is below the upper limit of the said range, the effect by components other than a fluorine-containing electrolyte polymer will be easy to express.
  • the content of the inorganic layered compound is preferably 0.2 to 20% by weight, more preferably 0.5 to 10% by weight, based on the total of the fluorine-containing electrolyte polymer, the inorganic layered compound and the silane compound X. 5 mass% is more preferable. If it is more than the lower limit of the said range, the cross leak of the fuel in a solid polymer electrolyte membrane will be fully suppressed easily. If it is below the upper limit of the said range, the fall of the proton conductivity of a solid polymer electrolyte membrane will be easy to be suppressed.
  • the content of the silane compound X is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass with respect to the total of the fluorine-containing electrolyte polymer, the inorganic layered compound, and the silane compound X. More preferably, it is 5 to 5% by mass. If it is more than the lower limit of the said range, it will be easy to fully disperse
  • the content of each component in the liquid composition can be determined from the liquid composition by a conventionally known analysis method, or can be calculated from the charged amount of each component when the liquid composition is produced. In the liquid composition, the content of the compound I calculated from the charged amount is equal to the content of the silane compound X.
  • the liquid composition may contain other components such as an additive having water retention and proton conductivity other than the fluorine-containing electrolyte polymer, the inorganic layered compound, and the silane compound X, and a reinforcing material.
  • the additive include silica, titania, zirconia, zirconium phosphate having no layered structure, phosphotungstic acid, phosphomolybdic acid, and silicotungstic acid.
  • the reinforcing material include glass fiber, ceramic fiber, quartz fiber, silica fiber, and polymer fiber. 30 mass% or less is preferable with respect to a liquid composition, and, as for content of another component, 10 mass% or less is more preferable.
  • the hydrolyzable silyl group-containing compound represented by the formula (I), the hydrolyzate of the hydrolyzable silyl group-containing compound, and the hydrolyzable silyl group-containing compound Compound condensate, hydrolyzable silyl group-containing compound represented by formula (II), hydrolyzate of the silyl group-containing compound, and condensate of the silyl group-containing compound, water represented by formula (I)
  • Special equipment such as an ultrasonic generator because it contains at least one silane compound selected from the group consisting of a condensate of a decomposable silyl group-containing compound and a hydrolyzable silyl group-containing compound represented by formula (II)
  • the inorganic layered compound can be easily dispersed in the liquid medium without using a high boiling point solvent without using a high boiling point solvent.
  • a solid polymer electrolyte membrane in which the inorganic layered compound is well dispersed in the fluorine-containing electrolyte polymer can be produced. Therefore, by using the liquid composition of the present invention, a solid polymer electrolyte membrane in which cross-leakage of fuel is suppressed can be easily produced.
  • the liquid composition of the present invention is a method for preparing a liquid composition by mixing a fluorine-containing electrolyte polymer, an inorganic layered compound, Compound I and / or Compound II, and a liquid medium.
  • the liquid medium, the fluorine-containing electrolyte polymer, the inorganic layered compound, and the compound I and / or compound II may be mixed at the same time; the mixed medium, the fluorine-containing electrolyte polymer, the inorganic layered compound
  • One or two compounds selected from the group consisting of a compound and / or compound II may be mixed, and the resulting mixed solution and the remaining components may be mixed together or sequentially.
  • an inorganic layered compound, Compound I and / or Compound II, and a liquid medium are mixed to prepare a mixed solution from the viewpoint that the inorganic layered compound can be satisfactorily dispersed in the liquid medium.
  • a fluorine-containing electrolyte polymer are preferably mixed; Compound I and / or Compound II and a liquid medium are mixed to prepare a first mixed solution, and the first mixed solution and the inorganic layered compound are mixed. It is preferable to prepare a second mixed solution and mix the second mixed solution and the fluorine-containing electrolyte polymer.
  • compound I and / or compound II in some cases, any one of a hydrolyzate of compounds I and II and a condensate of compounds I and II
  • the inorganic layered compound and the liquid medium are mixed, so that a special apparatus (such as an ultrasonic generator) is not used.
  • the inorganic layered compound can be easily dispersed in the liquid medium without using a high boiling point solvent.
  • the solid polymer electrolyte membrane of the present invention comprises a fluorine-containing electrolyte polymer; a hydrolyzable silyl group-containing compound represented by the formula (I), a hydrolyzate of the compound, a condensate of the compound, and the formula (II)
  • an inorganic layered compound or a reaction product of an inorganic layered compound and a silane compound also represents a case where both an inorganic layered compound and a reaction product of an inorganic layered compound and a silane compound are included.
  • the solid polymer electrolyte membrane of the present invention may contain a component other than the essential components and a reinforcing material as necessary.
  • the content of the fluorine-containing electrolyte polymer is preferably 70 to 99.7% by mass, more preferably 82 to 99.3% by mass, and still more preferably 90 to 98.5% by mass with respect to the solid polymer electrolyte membrane. If it is more than the lower limit of the said range, it will be easy to suppress the proton conductivity fall of a solid polymer electrolyte membrane. If it is below the upper limit of the said range, the effect by components other than a fluorine-containing electrolyte polymer will be easy to express.
  • the total content of the silane compound X, the inorganic stratiform compound, and the reaction product of the silane compound X and the inorganic stratiform compound is preferably 0.3 to 30% by mass based on the solid polymer electrolyte membrane. 7 to 18% by mass is more preferable, and 1.5 to 10% by mass is even more preferable. If it is more than the lower limit of the said range, the cross leak of the fuel in a solid polymer electrolyte membrane will be fully suppressed easily. If the total content of the inorganic layered compound, compound I, and reaction products derived therefrom is not more than the upper limit of the above range, a decrease in proton conductivity of the solid polymer electrolyte membrane can be easily suppressed.
  • the thickness of the solid polymer electrolyte membrane is preferably 1 to 25 ⁇ m, more preferably 2 to 15 ⁇ m, and even more preferably 3 to 10 ⁇ m. If it is more than the lower limit of the said range, the cross leak of the fuel in a solid polymer electrolyte membrane will be fully suppressed easily. In addition, the solid polymer electrolyte membrane is less likely to be wrinkled and not easily broken. If the amount is not more than the upper limit of the above range, the resistance of the solid polymer electrolyte membrane tends to be sufficiently low, so that it is easy to obtain a membrane electrode assembly with further excellent power generation performance.
  • the solid polymer electrolyte membrane may be reinforced with a reinforcing material.
  • the reinforcing material include porous bodies, fibers, woven fabrics, and nonwoven fabrics.
  • the reinforcing material include polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, polyethylene, polypropylene, polyphenylene sulfide, and the like.
  • the solid polymer electrolyte membrane of the present invention described above includes a hydrolyzable silyl group-containing compound represented by the formula (I) and / or the formula (II), a reaction product thereof, etc.
  • the inorganic layered compound is easily and satisfactorily dispersed in the fluorinated electrolyte polymer without using an apparatus (such as an ultrasonic generator) or without using a high-boiling solvent. Further, the shielding effect of the inorganic layered compound well dispersed in the fluorine-containing electrolyte polymer makes it difficult for hydrogen gas and methanol to permeate the solid polymer electrolyte membrane, thereby suppressing fuel cross leak.
  • the solid polymer electrolyte membrane in which the inorganic layered compound is well dispersed in the fluorine-containing electrolyte polymer has a high elastic modulus and is hard, the carbon fiber of the gas diffusion layer is difficult to penetrate, Short circuit is unlikely to occur.
  • the method for producing a solid polymer electrolyte membrane of the present invention is a method in which a liquid composition is prepared by the method for producing a liquid composition of the present invention and a solid polymer electrolyte membrane is formed using the liquid composition.
  • a method for forming a solid polymer electrolyte membrane using a liquid composition specifically, there is a method (cast method) in which the liquid composition is applied to the surface of a base film or a catalyst layer and dried. .
  • the drying temperature of the liquid composition when forming the solid polymer electrolyte membrane is preferably 10 to 95 ° C, more preferably 50 to 90 ° C.
  • the solid polymer electrolyte membrane is preferably heat-treated in order to reduce the degree of swelling when contacted with hot water.
  • the temperature of the heat treatment is preferably 110 to 220 ° C, more preferably 140 to 200 ° C. If it is more than the lower limit of the said range, the hot water tolerance of a solid polymer electrolyte membrane will be easy to improve. If it is below the upper limit of the said range, the thermal decomposition of an ion exchange group will be easy to be suppressed.
  • the solid polymer electrolyte membrane is subjected to a heat treatment at a temperature higher than 160 ° C., the dimensional change in the film surface direction is easily suppressed, the film does not easily wrinkle, and the mechanical durability is easily improved.
  • an inorganic layered compound and a compound containing a hydrolyzable silyl group-containing compound represented by the formula (I) and / or the formula (II) Since the liquid composition obtained by mixing with a liquid medium is used, a fluorine-containing electrolyte can be easily used without using a special apparatus (such as an ultrasonic generator) or using a high-boiling solvent.
  • a solid polymer electrolyte membrane in which the inorganic layered compound is well dispersed in the polymer and the cross leak of the fuel is suppressed can be produced.
  • the membrane electrode assembly of the present invention includes an anode having a catalyst layer, a cathode having a catalyst layer, and a solid polymer electrolyte membrane of the present invention disposed between the anode and the cathode.
  • FIG. 1 is a schematic cross-sectional view showing an example of a membrane electrode assembly.
  • the membrane electrode assembly 10 is in contact with the catalyst layer 11 between the anode 13 having the catalyst layer 11 and the gas diffusion layer 12, the cathode 14 having the catalyst layer 11 and the gas diffusion layer 12, and the anode 13 and the cathode 14. And a solid polymer electrolyte membrane 15 arranged in the above state.
  • the catalyst layer is a layer containing a catalyst and an electrolyte polymer.
  • the catalyst include a supported catalyst in which platinum or a platinum alloy is supported on a carbon support.
  • the carbon support include carbon black powder, graphitized carbon, carbon fiber, and carbon nanotube.
  • the electrolyte polymer include known electrolyte polymers used for the catalyst layer, and a polymer having a TFE unit and a unit (u1) is preferable from the viewpoint that a catalyst layer in which cracks are difficult to occur can be formed.
  • the gas diffusion layer has a function of uniformly diffusing gas in the catalyst layer and a function as a current collector.
  • Examples of the gas diffusion layer include carbon paper, carbon cloth, carbon felt and the like.
  • the gas diffusion layer is preferably subjected to water repellent treatment with polytetrafluoroethylene (hereinafter also referred to as PTFE) or the like.
  • the membrane electrode assembly 10 may have a carbon layer 16 between the catalyst layer 11 and the gas diffusion layer 12.
  • the carbon layer may be disposed between one of the catalyst layer of the anode and the cathode and the gas diffusion layer, or may be disposed between the catalyst layer of both the anode and the cathode and the gas diffusion layer.
  • the carbon layer is a layer containing carbon and a nonionic fluorine-containing polymer. Examples of carbon include carbon particles and carbon fibers. Carbon nanofibers having a fiber diameter of 1 to 1,000 nm and a fiber length of 1,000 ⁇ m or less are preferred. Examples of the nonionic fluorine-containing polymer include PTFE.
  • the membrane electrode assembly 10 may have an intermediate layer between the catalyst layer 11 and the gas diffusion layer 12.
  • the intermediate layer may be disposed between the catalyst layer 11 and the carbon layer 16.
  • the intermediate layer includes an electrolyte polymer and a carbon material. Examples of the electrolyte polymer include those similar to the electrolyte polymer contained in the catalyst layer and the solid polymer electrolyte membrane.
  • a polymer having a TFE unit and a unit (u1) is preferable.
  • carbon material carbon fiber is preferable.
  • carbon nanofibers are preferable. Examples of the carbon nanofiber include vapor grown carbon fiber, carbon nanotube (single wall, double wall, multiwall, cup laminated type, etc.) and the like.
  • the membrane / electrode assembly of the present invention is provided with a solid polymer electrolyte membrane that can suppress cross-leakage of fuel and can be easily manufactured.
  • a method for producing a membrane electrode assembly of the present invention comprises a membrane electrode assembly comprising an anode having a catalyst layer, a cathode having a catalyst layer, and a solid polymer electrolyte membrane disposed between the anode and the cathode.
  • a method for producing the solid polymer electrolyte membrane according to the method for producing a solid polymer electrolyte membrane of the present invention is a conventionally known method described in, for example, International Publication No. 2008/090990, International Publication No. 2009/116630, or the like, using the solid polymer electrolyte membrane obtained by the production method of the present invention. Can be manufactured.
  • middle layer can be formed on a gas diffusion layer by a conventionally well-known method, for example using the conventionally well-known thing of international publication 2009/116630.
  • a membrane / electrode assembly including a solid polymer electrolyte membrane that can be easily produced while suppressing cross-leakage of fuel can be produced.
  • a polymer electrolyte fuel cell can be obtained by arranging separators in which grooves or a large number of holes are formed on both surfaces of the membrane electrode assembly.
  • the separator include a separator made of various conductive materials such as a metal separator, a carbon separator, and a separator made of a material in which graphite and a resin are mixed.
  • power is generated by supplying a gas containing oxygen to the cathode and a gas containing hydrogen to the anode.
  • the membrane electrode assembly can also be applied to a methanol fuel cell that generates power by supplying methanol to the anode.
  • the fuel cell of the present invention includes a solid polymer electrolyte membrane that can suppress cross-leakage of fuel and can be easily manufactured.
  • the method for producing a polymer electrolyte fuel cell according to the present invention is a method for producing a polymer electrolyte fuel cell having a membrane electrode assembly, and the membrane electrode assembly is produced by the method for producing a membrane electrode assembly according to the present invention. Including a method of making a body. According to the method for producing a polymer electrolyte fuel cell of the present invention, it is possible to produce a polymer electrolyte fuel cell provided with a polymer electrolyte membrane that can suppress the cross leak of fuel and can be easily produced.
  • Examples 1 to 4 and 7 are examples, and examples 5 and 6 are comparative examples.
  • TQ TQ (unit: ° C.) is an index of the molecular weight and softening temperature of the polymer H, and when the polymer F is melt-extruded under the condition of an extrusion pressure of 2.94 MPa using a nozzle having a length of 1 mm and an inner diameter of 1 mm. This is the temperature at which the extrusion rate is 100 mm 3 / sec.
  • the extrusion amount of the polymer was measured using a flow tester CFT-500D (manufactured by Shimadzu Corporation).
  • the ion exchange capacity was determined by neutralizing polymer H with a 0.35N sodium hydroxide solution at 60 ° C. over 40 hours and titrating unreacted sodium hydroxide with 0.1N hydrochloric acid. .
  • the thickness of the solid polymer electrolyte membrane was measured by using a digimatic indicator (manufactured by Mitsutoyo, model number: 543-250, flat measurement terminal: ⁇ 5 mm), and the average thickness was measured. Say it.
  • SEM observation 1 The solid polymer electrolyte membrane was embedded with an epoxy resin, and cross-sectional processing was performed using a cross-sectional ion milling device (E-3500, manufactured by Hitachi High-Technologies Corporation). The processed electron beam was observed with a field emission scanning electron microscope (FE-SEM, manufactured by Hitachi High-Technologies Corporation, SU8230). The acceleration voltage was 2 kV.
  • the cross section of the solid polymer electrolyte membrane was observed with a scanning electron microscope (SEM) by the method of SEM observation 1 or 2, and the dispersibility of the inorganic layered compound was evaluated according to the following criteria.
  • SEM scanning electron microscope
  • ⁇ Each layer of the inorganic layered compound is separated and is well dispersed in the fluorine-containing electrolyte polymer in a state of being oriented in the surface direction of the solid polymer electrolyte membrane.
  • X The inorganic layered compound aggregates in the fluorine-containing electrolyte polymer, and a region where the inorganic layered compound does not exist is seen in the solid polymer electrolyte membrane.
  • the solid polymer electrolyte membrane was cut into 2 cm wide ⁇ 3 cm long and dried overnight under vacuum. Next, the horizontal and vertical dimensions and film thickness of the dried solid polymer electrolyte membrane were measured with a ruler. The film thickness was measured at three locations and the average value was calculated. 25 mL of 80 ° C. distilled water was added to a 50 mL capacity polyethylene jar, and the solid polymer electrolyte membrane whose dimensions were measured was immersed therein. The bottle was covered with an inner lid and allowed to stand in an oven at 80 ° C. for 16 hours in a sealed state.
  • the solid polymer electrolyte membrane was taken out of the bottle, and the length in the horizontal direction, the length in the vertical direction, and the film thickness at three locations were each measured on a wet filter paper.
  • the rate of change was calculated by comparing the dimensions before and after immersion (the length in the horizontal direction, the length in the vertical direction, and the average value of the film thickness).
  • the solid polymer electrolyte membrane to be evaluated was incorporated into a gas permeation device cell. Under conditions of 80 ° C., a cell effective gas permeation area of 3.3 cm 2 , and a gas flow rate of 30 cm 3 / min, a hydrogen gas having a controlled humidity is flowed to one surface side of the solid polymer electrolyte membrane, thereby Argon gas with adjusted humidity was flowed to the other surface side of the electrolyte membrane. Hydrogen gas permeating to the argon gas side was detected by gas chromatography, and the hydrogen gas permeation amount was measured.
  • Polymer (H-1) was prepared by subjecting polymer (F-1), which is a copolymer of TFE and CF 2 ⁇ CFOCF 2 CF (CF 3 ) OCF 2 CF 2 SO 2 F (TQ 225 ° C.), to alkaline hydrolysis by a known method. After the decomposition, the polymer is treated with an acid to convert the —SO 2 F group of the polymer (F-1) into an —SO 3 H group.
  • a mixed solvent of water / ethanol 40/60 (mass ratio) that has passed through a filter with a pore size of 5 ⁇ m, and stir 1 on the stirrer. Stirring was performed for about a minute.
  • the liquid composition is placed in a petri dish (75 mm ⁇ ) made of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (hereinafter referred to as PFA), left to stand at room temperature in a dark place for 3 to 7 days, and dried. It was. Thereby, a film was formed on the petri dish.
  • the obtained membrane was peeled from the petri dish with tweezers, sandwiched between 10 cm square PTFE sheets, and heated at 160 ° C. for 30 minutes to obtain a solid polymer electrolyte membrane.
  • a heating means a manual hydraulic heating press (manufactured by Imoto Seisakusho, 180C [IMC-180C type]) was used. Table 1 shows the evaluation results of the thickness and dispersibility of the obtained solid polymer electrolyte membrane.
  • An SEM photograph of a cross section of the solid polymer electrolyte membrane observed under the conditions of SEM observation 1 is shown in FIG.
  • a solid polymer electrolyte membrane was obtained in the same manner as in Example 1 except for changing to. Table 1 shows the evaluation results of the thickness and dispersibility of this solid polymer electrolyte membrane.
  • An SEM photograph of a cross section of the solid polymer electrolyte membrane observed under the conditions of SEM observation 1 is shown in FIG.
  • FIG. 5 shows an SEM photograph of a cross section of the solid polymer electrolyte membrane observed under the conditions of SEM observation 1.
  • Example 4 The liquid composition contained in the PFA petri dish was allowed to stand in an oven at 85 ° C. for 3 to 4 hours and dried, and then heat-treated at 180 ° C. for 1 hour. A molecular electrolyte membrane was obtained. Table 1 shows the evaluation results of the thickness and dispersibility of this solid polymer electrolyte membrane, the dimensional change rate, and Table 3 shows the hydrogen gas permeability coefficient.
  • Example 5 A solid polymer electrolyte membrane was obtained in the same manner as in Example 1 except that the compound (I-1) and the inorganic layered compound were not used and the heat treatment conditions were the same as in Example 2.
  • Table 2 shows the thickness and dimensional change rate of the solid polymer electrolyte membrane.
  • Example 6 A solid polymer electrolyte membrane was obtained in the same manner as in Example 4 except that 30 mg of the inorganic layered compound was added without using compound (I-1), and then stirred on a stirrer at 1000 rpm for about 1 minute.
  • Table 2 shows the evaluation results of the thickness and dispersibility of the solid polymer electrolyte membrane.
  • An SEM photograph of a cross section of the solid polymer electrolyte membrane observed under the conditions of SEM observation 2 is shown in FIG.
  • Table 4 shows the hydrogen gas permeability coefficient of the solid polymer electrolyte membrane.
  • Example 7 A solid polymer electrolyte membrane was obtained in the same manner as in Example 1 except that it was allowed to stand in an oven at 85 ° C. for 3 to 4 hours to dry and then heat-treated at 160 ° C. for 1 hour.
  • Table 2 shows the evaluation results of the thickness dispersibility of this solid polymer electrolyte membrane and the dimensional change rate.
  • Example 8 Solid polymer electrolyte of polymer (H-1) obtained by coating dispersion A on a substrate without adding compound (I-1) and the inorganic layered compound and heat-treating at 160 ° C. for 30 minutes The hydrogen gas permeability coefficient of the membrane (thickness 50 ⁇ m) was determined.
  • Table 3 shows (hydrogen gas permeability coefficient ratio).
  • Table 4 shows the ratio of the hydrogen gas permeability coefficient of the solid polymer electrolyte membrane of Example 6 to the hydrogen gas permeability coefficient of the solid polymer electrolyte membrane obtained in Example 8.
  • the hydrogen gas permeation coefficient of the solid polymer electrolyte membrane of Example 4 to which the inorganic layered compound and the compound (I-1) were added at all humidity was determined by the solid polymer of the polymer (H-1). It was suppressed to less than 40% of the hydrogen gas permeability coefficient of the electrolyte membrane.
  • the hydrogen gas permeability coefficient of the solid polymer electrolyte membrane of Example 6 was in spite of the addition of the inorganic layered compound.
  • the hydrogen gas permeation coefficient of the polymer (H-1) solid polymer electrolyte membrane was limited to about 60%.
  • the solid polymer electrolyte membrane of the present invention is a solid polymer electrolyte membrane in a membrane electrode assembly for a polymer electrolyte fuel cell; a proton selective permeable membrane used for water electrolysis, hydrogen peroxide production, ozone production, waste acid recovery, etc .; It is useful as a cation exchange membrane for salt electrolysis; a redox flow battery membrane; a cation exchange membrane for electrodialysis used for desalting or salt production.

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Abstract

L'invention concerne : une composition liquide qui permet de produire facilement une membrane électrolytique polymère solide pour laquelle une fuite traversante d'un combustible est supprimée; une membrane électrolytique polymère solide; et un ensemble membrane-électrode. Plus précisément, l'invention concerne une composition liquide contenant un polymère électrolytique contenant du fluor, un composé lamellaire inorganique, un milieu liquide et au moins un composé silane choisi dans le groupe constitué par les composés contenant un groupe silyle hydrolysable de formule (I), les produits d'hydrolyse de ceux-ci, les produits de condensation de ceux-ci, les composés contenant un groupe silyle hydrolysable de formule (II), les produits d'hydrolyse de ceux-ci, les produits de condensation de ceux-ci et les produits de condensation des composés contenant un groupe silyle hydrolysable représentés par la formule (I) et des composés contenant un groupe silyle hydrolysable représentés par la formule (II); une membrane électrolytique polymère solide qui est obtenue à partir de cette composition liquide; un ensemble membrane-électrode; et similaires. Rf-(CH2)k-SiLmR2 3-m (II) (dans la formule, Rf représente un groupe organique monovalent contenant F; R1 représente H ou un groupe alkyle; Q représente une liaison simple ou un groupe alkylène lorsque p vaut 0 et représente un groupe alkylène lorsque p vaut 1; L représente un groupe hydrolysable; R2 représente H ou un groupe hydrocarboné monovalent; p vaut 0 ou 1; m représente un nombre de 1 à 3; n représente un nombre de 1 à 6; et k représente un nombre de 1 à 3.)
PCT/JP2018/005497 2017-02-16 2018-02-16 Composition liquide, membrane électrolytique polymère solide et ensemble membrane-électrode Ceased WO2018151254A1 (fr)

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