Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
  • H01M8/1018—Polymeric electrolyte materials
  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
• • 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
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• • 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
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
  • H01M4/8668—Binders
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/88—Processes of manufacture
  • H01M4/8803—Supports for the deposition of the catalytic active composition
  • H01M4/8807—Gas diffusion layers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/88—Processes of manufacture
  • H01M4/8803—Supports for the deposition of the catalytic active composition
  • H01M4/881—Electrolytic membranes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/88—Processes of manufacture
  • H01M4/8825—Methods for deposition of the catalytic active composition
  • H01M4/8828—Coating with slurry or ink
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/90—Selection of catalytic material
  • H01M4/92—Metals of platinum group
  • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
  • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
• • 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
  • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
• • 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
  • H01M2008/1095—Fuel cells with polymeric electrolytes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells

Definitions

• the present invention relates to a polymer compound having a sulfonic acid group, a catalyst composition containing the compound, and a polymer electrolyte fuel cell using the compound.
• a polymer electrolyte fuel cell has an anode catalyst layer, a cathode catalyst layer, and a solid electrolyte membrane sandwiched between both catalyst layers. Electrolytes used in solid electrolyte membranes are required to have proton conductivity, gas barrier properties, electronic insulation properties, and durability. Fluorine-based ionomers are used as electrolytes that meet these characteristics.
• Hydrocarbon ionomers having an aromatic skeleton and having a sulfonic acid group introduced into the skeleton are known as electrolytes used in solid electrolyte membranes and catalyst layers (see, for example, Patent Document 1 and Patent Document 2).
• a composition used for a solid electrolyte membrane a composition containing a fluorinated polymer having a sulfonic acid group and a fluorinated aromatic compound having a functional group capable of reacting with the sulfonic acid group of this fluorinated polymer is known ( For example, see Patent Document 3).
• a first aspect of the present invention aims to provide a catalyst composition that, when used in a catalyst layer of a polymer electrolyte fuel cell, allows the polymer electrolyte fuel cell to exhibit good power generation characteristics.
• a second aspect of the present invention aims to provide a compound that, when used as an electrolyte in a catalyst layer of a polymer electrolyte fuel cell, allows the polymer electrolyte fuel cell to exhibit good power generation characteristics.
• n is 1 to 2
• o is 1 to 3
• p is 0 to 3
• Ring A is a benzene ring or a naphthalene ring
• B and C are each independently a group in which at least one member selected from the group consisting of an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, and an aromatic group is bonded to ring A via a single heteroatom; , or a heterocycle in which the heteroatom in the ring is bonded to ring A, and the rings and groups of B and C may have substituents, B and C may be the same or different, at least one of them has an aromatic ring, and at least one of the aromatic rings of B and C has at least one
• R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, or an aromatic group which may have a substituent, and R 1 and R 2 are (They may form a ring together.)
• the structures represented by B and C are each independently represented by the following general formula (IV) or (V), and are included in the general formula (IV) or (V).
• the rings and groups may have a substituent, and at least one of the aromatic rings of general formula (IV) or (V) has a structure having at least one sulfonic acid group [1] to [3] ] Any catalyst composition.
• Ar 2 and Ar 3 are each independently a benzene ring or a naphthalene ring which may have a substituent, and Y is a single bond, -CH 2 - or carbonyl.
• R4 is an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, a phenyl group or a naphthyl group, which may have a substituent; R 3 and R 4 may be combined with each other to form a ring containing X, and at least one of the aromatic rings of B has at least one sulfonic acid group,
• R 3 and R 4 each independently represent a substituent.
• R 3 and R 4 are a structure that may be combined with each other to form a ring containing X. 4] to [6].
• a catalyst layer of a polymer electrolyte fuel cell comprising the catalyst composition of [8].
• a membrane electrode assembly having a solid electrolyte membrane, a gas diffusion layer, and the catalyst layer of [9].
• a polymer electrolyte fuel cell having the membrane electrode assembly of [10].
• Ring A is a benzene ring or a naphthalene ring
• B and C are each independently a group in which at least one member selected from the group consisting of an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, and an aromatic group is bonded to ring A via a single heteroatom; , or a heterocycle in which the heteroatom in the ring is bonded to ring A, and the rings and groups of B and C may have substituents, B and C may be the same or different, at least one of them has an aromatic ring, and at least one of the aromatic rings of B and C has at least one sulfonic acid group, Carbons in ring A other than the carbons bonded to the main chain and the carbons bonded to B and C may be substituted with halogen atoms.
• R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, or an aromatic group which may have a substituent, and R 1 and R 2 are (They may form a ring together.)
• the polymer compound of [14] used as an electrolyte for an anode catalyst layer and/or a cathode catalyst layer of a polymer electrolyte fuel cell.
• a catalyst layer for a polymer electrolyte fuel cell comprising the compound of [14] or [15].
• the polymer electrolyte fuel cell When the catalyst composition of the first aspect of the present invention is used in the catalyst layer of a polymer electrolyte fuel cell, the polymer electrolyte fuel cell exhibits good power generation characteristics.
• the compound of the second aspect of the present invention is used as an electrolyte in the catalyst layer of a polymer electrolyte fuel cell, the polymer electrolyte fuel cell exhibits good power generation characteristics.
• FIG. 1 is a cross-sectional view schematically showing the configuration of a polymer electrolyte fuel cell.
• an ionomer refers to a polymer material having a proton conduction function.
• a first aspect of the present invention is a catalyst composition containing a polymer compound having a structure represented by the following general formula (I), a catalyst, and a catalyst carrier.
• n is 1 to 2
• o is 1 to 3
• p is 0 to 3
• Ring A is a benzene ring or a naphthalene ring
• B and C are each independently a group in which at least one member selected from the group consisting of an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, and an aromatic group is bonded to ring A via a single heteroatom; , or a heterocycle in which the heteroatom in the ring is bonded to ring A, and the rings and groups of B and C may have substituents, B and C may be the same or different, at least one of them has an aromatic ring, and at least one of the aromatic rings of B and C has at least one sulfonic acid group, Carbons in ring A other than the carbons bonded to the main chain and the carbons bonded to B and C may be substituted with halogen atoms.
• FIG. 1 is a cross-sectional view schematically showing the configuration of a polymer electrolyte fuel cell (hereinafter also referred to as "fuel cell”).
• the polymer electrolyte fuel cell 100 includes an anode catalyst layer 103, a cathode catalyst layer 105, and a solid electrolyte membrane 107 sandwiched between the two catalyst layers, and each catalyst layer has a gas diffusion layer (hereinafter referred to as "Gas Diffusion Layer”) on the outside. (also referred to as "GDL”) 101.
• Gas Diffusion Layer gas diffusion layer
• This configuration is called a membrane electrode assembly (hereinafter also referred to as "MEA”).
• this membrane electrode assembly (MEA) is usually sandwiched between separators 109 .
• a catalyst supported on a catalyst carrier is called an electrode catalyst.
• the anode catalyst layer 103 and/or the cathode catalyst layer 105 may be abbreviated as a catalyst layer.
• At least one of the anode catalyst layer 103 and the cathode catalyst layer 105 of the fuel cell contains a catalyst composition containing a polymer compound having a structure represented by the following general formula (I), a catalyst, and a catalyst carrier, and From the viewpoint of suppressing an increase in overvoltage due to a decrease in oxygen gas diffusivity during current driving, it is preferable that at least the cathode catalyst layer 105 contains the catalyst composition of the first embodiment.
• the catalyst composition contains a polymer compound having a structure represented by the following general formula (I).
• a polymer compound having a structure represented by the following general formula (I) is used as an electrolyte.
• n is 1 to 2
• o is 1 to 3
• p is 0 to 3
• Ring A is a benzene ring or a naphthalene ring
• B and C are each independently a group in which at least one member selected from the group consisting of an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, and an aromatic group is bonded to ring A via a single heteroatom; , or a heterocycle in which the heteroatom in the ring is bonded to ring A, and the rings and groups of B and C may have substituents, B and C may be the same or different, at least one of them has an aromatic ring, and at least one of the aromatic rings of B and C has at least one sul
• the polymer compound having the structure represented by general formula (I) preferably has a weight average molecular weight of 8,000 to 500,000 as measured by the gel permeation chromatography method described in the examples, and preferably has a weight average molecular weight of 8,000 to 500,000, and ,000 to 200,000, and even more preferably 20,000 to 120,000.
• n is 1 to 2, preferably 2.
• ring A is a benzene ring or a naphthalene ring, preferably a benzene ring.
• general formula (I) is represented by the following general formula (i).
• carbon, B, C, n, o and p of ring A are as defined in general formula (I).
• the weight average molecular weight of the polymer compound having the structure represented by general formula (i) is the same as that of the polymer compound having the structure represented by general formula (I).
• B and C are each independently at least one selected from the group consisting of an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, and an aromatic group.
• ring A through a heteroatom, preferably through an oxygen atom, a sulfur atom or a nitrogen atom, more preferably through one selected from the group consisting of -O-, -S- and -N-. It is a heterocycle in which a bonding group or a heteroatom in the ring is bonded to ring A.
• “Through a single heteroatom” means through a linker consisting of one heteroatom, and does not include the case through a linker consisting of two or more heteroatoms such as -SO 2 -. At least one selected from the group consisting of an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, and an aromatic group is preferably directly bonded to a hetero atom.
• "directly” means, for example, that no hydrocarbon chain or the like is included between the aromatic group and the atom.
• B and C are each independently a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkyl group having 1 to 16 carbon atoms, or an alkyl group having 1 to 16 carbon atoms; A group in which at least one selected from the group consisting of a cycloalkyl group, a phenyl group, and a naphthyl group is bonded to ring A through a single heteroatom, or a heteroatom in the ring is bonded to ring A, and benzene A heterocyclic ring containing one selected from the group consisting of a ring, a naphthalene ring, and an ether bond is preferable.
• the rings and groups of B and C may have substituents.
• B and C may be the same or different, at least one of them has an aromatic ring, and at least one of the aromatic rings of B and C has at least one sulfonic acid group.
• the heteroatom in B and C is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, more preferably a sulfur atom or a nitrogen atom, and even more preferably a nitrogen atom.
• one selected from the group consisting of -O-, -S- and -N- is preferably -S- or -N-, more preferably -S-.
• each of the substituents if there are multiple, is an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms. is preferably an alkoxy group.
• the structures represented by B and C are each independently represented by the following general formula (IV) or (V), and are included in general formula (IV) or (V).
• the rings and groups may have substituents, and it is preferable that at least one of the aromatic rings in general formula (IV) or (V) has at least one sulfonic acid group.
• Ar 2 and Ar 3 are each independently a benzene ring or a naphthalene ring which may have a substituent, and Y is a single bond, -CH 2 - or carbonyl; , q is 0 or 1, and when q is 0, one terminal of Y and N (nitrogen atom) are connected.
• each is preferably independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
• X is a heteroatom
• R 3 and R 4 are each independently an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, a phenyl group or a naphthyl group, which may have a substituent, preferably , a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 1 to 16 carbon atoms, a phenyl group, or It is a naphthyl group.
• R 3 and R 4 may be combined with each other to form an X-containing ring.
• each is preferably independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
• Y is preferably a single bond.
• X is preferably a sulfur atom or a nitrogen atom.
• Examples of the structure represented by general formula (IV) include structures represented by general formula (VI) or (VII) below, in which at least one of the aromatic rings has at least one sulfonic acid group. It will be done.
• Y is a single bond, -CH 2 - or carbonyl, q is 0 or 1, and when q is 0, one terminal of Y and N (nitrogen atom) is s is an integer of 1 to 6, and R 5 is each independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. be. It is preferable that Y is a single bond.
• r is an integer of 1 to 5
• s is an integer of 1 to 6
• R 5 is each independently an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms; is a haloalkyl group or an alkoxy group having 1 to 3 carbon atoms.
• Examples of the structure which is a group, an alkyl group having an ether bond, or a cycloalkyl group include a structure represented by the following general formula (XI), in which the aromatic ring has at least one sulfonic acid group.
• r is an integer of 1 to 5
• R 5 is each independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms
• R 6 has a linear or branched alkyl group having 1 to 16 carbon atoms, which may have a substituent R 5 , or a linear or branched ether bond having 1 to 16 carbon atoms. It is an alkyl group or a cycloalkyl group having 1 to 16 carbon atoms.
• the following general formula (XIV) has a structure in which R 3 and R 4 in the general formula (V) are alkyl groups having an ether bond, and together form a ring containing X.
• R 6 is each independently a substituent selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms.
• a straight-chain or branched alkyl group having 1 to 12 carbon atoms a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or a straight-chain or branched alkyl group having 1 to 12 carbon atoms, which may have It is a cycloalkyl group.
• r is an integer of 1 to 5
• R 5 is each independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
• t is an integer of 1 to 6.
• B and C may be the same, but are preferably different.
• structures of the general formulas (VI), (VIII), and (IX) are preferred, in which at least one of the aromatic rings has at least one sulfonic acid group.
• the structures of the general formulas (VI) to (XIV) are the same, and only the substituents other than the sulfonic acid group are different, and at least one of the aromatic rings Also preferred are structures in which each has at least one sulfonic acid group.
• B and C are different, in general formulas (I) and (i), p is not 0, and B has a structure represented by the above general formula (IV), or the above general formula (V ), R 3 is a phenyl group or naphthyl group which may have a substituent, and R 4 is an alkyl group or an ether bond which may have a substituent.
• R 3 and R 4 may be combined with each other to form a ring containing X, and the aromatic At least one of the rings has at least one sulfonic acid group, and C is a structure in which R 3 and R 4 each independently have a substituent in the structure represented by the general formula (V).
• B is selected from the group consisting of the general formulas (VI) to (XI), and at least one of its aromatic rings has at least one sulfonic acid group
• C is a structure represented by the general formula ( More preferably, it is selected from the group consisting of XII) to (XIV). With such a structure, the amount of sulfonic acid groups introduced into the polymer compound having the structure represented by general formula (I) can be adjusted.
• the polymer compound having the structure represented by general formula (I) is preferably a compound represented by general formula (II).
• the compound represented by the general formula (II) is more preferably a compound represented by the following general formula (ii).
• rings A, B, C, n, o and p are as defined in general formula (I).
• carbon, B, C, n, o and p of ring A are as defined in general formula (I).
• m is 3 or more, preferably 3 to 100, more preferably 15 to 60.
• Ar 1 is an aromatic group having 6 to 40 carbon atoms and which may have a substituent. Note that the number of carbon atoms includes the number of carbon atoms of substituents. Examples of the aromatic group include divalent groups such as benzene, naphthalene, acetylene, biphenyl, indacene, biphenylene, acenaphthylene, acenaphthene, fluorene, phenalene, phenanthrene, tetralin, and anthracene. Examples of the substituent include the same substituents as R 1 and R 2 in the following general formula (III), each independently when there is a plurality of substituents. Ar 1 has a structure different from that represented by general formula (I). In the general formulas (II) and (ii), it is preferable that Ar 1 has a structure represented by the following general formula (III).
• R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, or an aromatic group that may have a substituent, and preferably have no substituent.
• R 1 and R 2 may be combined with each other to form a ring.
• each is preferably independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, and/or an alkoxy group having 1 to 3 carbon atoms.
• the ion exchange capacity (IEC (mmol/g)) of the polymer compound having the structure represented by general formulas (I) and (i) is preferably 0.1 to 6, more preferably 1 to 5, and 1.5 -4 is more preferred.
• the number of sulfonic acid groups in the polymer compound having the structure represented by general formula (I) is preferably such that the ion exchange capacity falls within the above range.
• ring A of general formulas (I) and (i) carbons other than the carbons bonded to the main chain and the carbons bonded to B and C may be substituted with halogen atoms.
• the main chain is the main chain of a polymer compound having a structure represented by general formula (I).
• the halogen atom a fluorine atom is preferred.
• the number of halogen atoms substituted in ring A is preferably 0 to 5 per ring A, more preferably 0 to 3.
• the polymer compound having the structure represented by the general formula (I) can be produced by the following production method, for example, with reference to the non-patent document Macromolecules 2013, 46, 370-374.
• ring A is the same as the definition of general formula (I)
• n, o, p are the same as the definition of general formula (I)
• Ar 1 and m are the same as defined in general formula (II)
• B' and C' are the same as defined in general formula (I) B and C, except that they do not have a sulfonic acid group.
• a brominated compound of Ar 1 and a compound to be ring A are mixed with a metal such as tris(dibenzylideneacetone)dipalladium(0) in a solvent such as cyclopentyl methyl ether.
• a metal such as tris(dibenzylideneacetone)dipalladium(0)
• a solvent such as cyclopentyl methyl ether.
• the reaction is carried out in the presence of the catalysts tris-o-methoxyphenyl)phosphine, cesium carbonate and pivalic acid.
• the reaction temperature is usually 100 to 110°C.
• the solvent used in this reaction only needs to be able to dissolve the raw materials, and in addition to cyclopentyl methyl ether, dimethylacetamide, toluene, etc. can be used.
• metal catalysts include palladium(II) acetic acid, tris(dibenzylideneacetone)dipalladium(0) (chloroform adduct), chloro[(tri-tert-butyl) phosphine)-2-(2-aminobiphenyl)]palladium(II), trans-di( ⁇ -acetato)bis[o-di-o-tolylphosphinobenzyldipalladium(II) can be used.
• the compound obtained by (Formula 1) and B' and C' are The reaction is carried out in the presence of a base such as potassium carbonate in an N,N-dimethylformamide solvent, and B' and C' are introduced into ring A of the compound obtained by (Formula 1).
• a base such as potassium carbonate
• B' and C' are introduced into ring A of the compound obtained by (Formula 1).
• the introduction ratio of B' and C' can be controlled by the amounts of B' and C' added.
• the reaction temperature is usually 110 to 130°C.
• As the base in addition to potassium carbonate, sodium hydride, potassium tert-butoxide, or diazabicycloundensen can be used.
• the compound thus obtained is reacted with a sulfonating agent in a dichloromethane solvent to introduce at least one sulfonic acid group into at least one of the aromatic rings possessed by B' and C'. Make it C.
• a sulfonic acid group is selectively introduced into any position of the aromatic ring possessed by B' and C', which has less steric hindrance than Ar 1 (the above-mentioned fluorene skeleton-containing unit) constituting the main chain.
• the reaction temperature is usually 25 to 35°C.
• the sulfonating agent include trimethylsilylchlorosulfonate, chlorinated sulfonic acid, fuming sulfuric acid, sulfuric acid, and the like.
• metal catalysts include metals such as platinum, gold, silver, ruthenium, iridium, rhodium, palladium, osmium, tungsten, lead, iron, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, and aluminum; Examples include alloys, core shells thereof, and the like. Examples of nonmetallic catalysts include carbon alloy catalysts.
• a carbon alloy catalyst is a carbon material obtained by heating and carbonizing a raw material containing an organic material and a metal, and is known to exhibit catalytic activity.
• the organic material is not particularly limited as long as it can be carbonized, and examples thereof include thermosetting resins such as melamine resin, epoxy resin, and phenol resin.
• thermosetting resins such as melamine resin, epoxy resin, and phenol resin.
• metal any known metal can be used without particular limitation, and examples thereof include iron, cobalt, titanium, and the like.
• Catalyst carrier examples include carbon black such as channel black, furnace black, and thermal black, carbon nanotubes, activated carbon obtained by carbonizing and activating materials containing various carbon atoms, coke, natural graphite, artificial graphite, and graphitized carbon. Examples include carbon materials, and carbon black is preferred because it has a high specific surface area and excellent electronic conductivity.
• a polymer compound having a structure represented by the above general formula (I) is used.
• a polymer compound having a structure represented by the general formula (I) may be used alone, and the compound represented by the general formula (I) may optionally be supplemented with other electrolytes, such as Fluorinated sulfonic acids such as Nafion (registered trademark, manufactured by DuPont Corporation), Aquivion (registered trademark, manufactured by Solvay Corporation), Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.), Aciplex (registered trademark, manufactured by Asahi Kasei Corporation), etc. At least one selected from the group consisting of a polymer, a hydrocarbon sulfonic acid polymer, and a partially fluorinated hydrocarbon sulfonic acid polymer may be combined.
• a method for producing the anode catalyst layer 103 and cathode catalyst layer 105 will be described.
• the catalyst ink is applied onto a target substrate and dried. Create a catalyst layer.
• the catalyst composition contains, as an electrolyte, an electrolyte other than the polymer compound having the structure represented by the general formula (I). You may
• the target base material examples include a polymer electrolyte membrane, GDL, a sheet made of fluororesin, and the like, and the catalyst layer can be produced by a known manufacturing method.
• a catalyst ink is applied to a sheet made of fluororesin, the applied catalyst layer is transferred to a polymer electrolyte membrane.
• a sheet made of polytetrafluoroethylene (PTFE) is generally used as a sheet made of fluororesin.
• the polymer compound having the structure represented by the general formula (I) can coat the catalyst supported on the catalyst carrier with an appropriate thickness, thereby improving gas diffusivity and improving gas diffusivity while maintaining the catalyst function. Good proton conductivity.
• the amount of the polymer compound having the structure represented by the above general formula (I) to be used is preferably 0.1 to 10 times the amount of the catalyst.
• the catalyst composition used as the catalyst ink may include a binder and a solvent.
• the binder can be used as a component that binds catalyst carriers to each other in order to suppress a decrease in electron conductivity in the electrode catalyst.
• the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene-propylene-diene copolymer (EPDM), Nafion (registered trademark, manufactured by DuPont Corporation), and Aquivion (registered trademark).
• fluorine-based sulfonic acid polymers such as Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.), Aciplex (registered trademark, manufactured by Asahi Kasei Corporation), and the like. These may be used alone or in combination of two or more.
• the solvent examples include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, pentanol, dimethyl sulfoxide, N,N-dimethylformamide, etc.
• Examples include polar solvents.
• the solvent is preferably water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and isobutyl alcohol. These may be used alone or in combination of two or more.
• the content of each component in the catalyst composition is adjusted appropriately depending on the purpose, but in the catalyst composition, the content of the catalyst is 10 to 60% by mass in 100% by mass of the solid content excluding the weight of the solvent. is preferably 30 to 50% by mass, and the electrolyte containing the polymer compound having the structure represented by the general formula (I) is preferably 5 to 50% by mass, more preferably 10 to 30% by mass,
• the catalyst carrier is preferably 20 to 75% by mass, more preferably 30 to 50% by mass, and the binder is preferably 0 to 5% by mass, more preferably 0 to 3% by mass.
• the components listed as both the electrolyte and the binder are included in the electrolyte in the above blending amounts.
• the solvent used in the catalyst composition is preferably 50 to 99% by mass, more preferably 80 to 99% by mass, based on 100% by mass of the catalyst composition.
• Materials for the solid electrolyte membrane 107 include polymer compounds having the structure represented by the general formula (I), Nafion (registered trademark, manufactured by DuPont Corporation), Aquivion (registered trademark, manufactured by Solvay Corporation), and Flemion (registered trademark, manufactured by Solvay Corporation).
• Examples include fluorine-based sulfonic acid polymers, hydrocarbon-based sulfonic acid polymers, and partially fluorinated hydrocarbon-based sulfonic acid polymers such as Aciplex (registered trademark, manufactured by Asahi Glass Co., Ltd.) and Aciplex (registered trademark, manufactured by Asahi Kasei Corporation). From the viewpoint of proton conductivity, examples include compounds represented by the above general formula (I).
• the thickness of the solid electrolyte membrane 107 is preferably 10 to 100 ⁇ m, more preferably 20 to 60 ⁇ m, from the viewpoints of conductivity, durability, and gas cross leakage.
• the gas diffusion layer 101 is not particularly limited, but a porous material having electrical conductivity is preferably used, and examples of such materials include carbon paper, nonwoven fabric, felt, nonwoven fabric, etc. .
• a second aspect of the present invention is a polymer compound having a structure represented by the following general formula (I).
• n is 1 to 2
• o is 1 to 3
• p is 0 to 3
• Ring A is a benzene ring or a naphthalene ring
• B and C are each independently a group in which at least one member selected from the group consisting of an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, and an aromatic group is bonded to ring A via a single heteroatom; , or a heterocycle in which the heteroatom in the ring is bonded to ring A, and the rings and groups of B and C may have substituents, B and C may be the same or different, at least one of them has an aromatic ring, and at least one of the aromatic rings of B and C has at least one sulfonic acid group, Carbons in ring A other
• the polymer compound having the structure represented by general formula (I) preferably has a weight average molecular weight of 8,000 to 500,000 as measured by the gel permeation chromatography method described in the examples, and preferably has a weight average molecular weight of 8,000 to 500,000, and ,000 to 200,000, and even more preferably 20,000 to 120,000.
• n is 1 to 2, preferably 2.
• ring A is a benzene ring or a naphthalene ring, preferably a benzene ring.
• general formula (I) is represented by the following general formula (i).
• carbon, B, C, n, o and p of ring A are as defined in general formula (I).
• the weight average molecular weight of the polymer compound having the structure represented by general formula (i) is the same as that of the polymer compound having the structure represented by general formula (I).
• B and C are each independently at least one selected from the group consisting of an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, and an aromatic group.
• ring A through a heteroatom, preferably through an oxygen atom, a sulfur atom or a nitrogen atom, more preferably through one selected from the group consisting of -O-, -S- and -N-. It is a heterocycle in which a bonding group or a heteroatom in the ring is bonded to ring A.
• “Through a single heteroatom” means through a linker consisting of one heteroatom, and does not include the case through a linker consisting of two or more heteroatoms such as -SO 2 -. At least one selected from the group consisting of an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, and an aromatic group is preferably directly bonded to a hetero atom.
• "directly” means, for example, that no hydrocarbon chain or the like is included between the aromatic group and the atom.
• B and C are each independently a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkyl group having 1 to 16 carbon atoms, or an alkyl group having 1 to 16 carbon atoms; A group in which at least one selected from the group consisting of a cycloalkyl group, a phenyl group, and a naphthyl group is bonded to ring A through a single heteroatom, or a heteroatom in the ring is bonded to ring A, and benzene A heterocyclic ring containing one selected from the group consisting of a ring, a naphthalene ring, and an ether bond is preferable.
• the rings and groups of B and C may have substituents.
• B and C may be the same or different, at least one of them has an aromatic ring, and at least one of the aromatic rings of B and C has at least one sulfonic acid group.
• the heteroatom in B and C is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, more preferably a sulfur atom or a nitrogen atom, and even more preferably a nitrogen atom.
• one selected from the group consisting of -O-, -S- and -N- is preferably -S- or -N-, more preferably -S-.
• each of the substituents is an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms. is preferably an alkoxy group.
• the structures represented by B and C are each independently represented by the following general formula (IV) or (V), and are included in general formula (IV) or (V).
• the rings and groups may have substituents, and it is preferable that at least one of the aromatic rings in general formula (IV) or (V) has at least one sulfonic acid group.
• Ar 2 and Ar 3 are each independently a benzene ring or a naphthalene ring which may have a substituent, and Y is a single bond, -CH 2 - or carbonyl; , q is 0 or 1, and when q is 0, one terminal of Y and N (nitrogen atom) are connected.
• each is preferably independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
• X is a heteroatom
• R 3 and R 4 are each independently an alkyl group, an alkyl group having an ether bond, a cycloalkyl group, a phenyl group or a naphthyl group, which may have a substituent, preferably , a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 1 to 16 carbon atoms, a phenyl group, or It is a naphthyl group.
• R 3 and R 4 may be combined with each other to form an X-containing ring.
• each is preferably independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
• Y is preferably a single bond.
• X is preferably a sulfur atom or a nitrogen atom.
• Examples of the structure represented by general formula (IV) include structures represented by general formula (VI) or (VII) below, in which at least one of the aromatic rings has at least one sulfonic acid group. It will be done.
• Y is a single bond, -CH 2 - or carbonyl, q is 0 or 1, and when q is 0, one terminal of Y and N (nitrogen atom) is s is an integer of 1 to 6, and R 5 is each independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. be. It is preferable that Y is a single bond.
• r is an integer of 1 to 5
• s is an integer of 1 to 6
• R 5 is each independently an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms; is a haloalkyl group or an alkoxy group having 1 to 3 carbon atoms.
• Examples of the structure which is a group, an alkyl group having an ether bond, or a cycloalkyl group include a structure represented by the following general formula (XI), in which the aromatic ring has at least one sulfonic acid group.
• r is an integer of 1 to 5
• R 5 is each independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms
• R 6 has a linear or branched alkyl group having 1 to 16 carbon atoms, which may have a substituent R 5 , or a linear or branched ether bond having 1 to 16 carbon atoms. It is an alkyl group or a cycloalkyl group having 1 to 16 carbon atoms.
• the following general formula (XIV) has a structure in which R 3 and R 4 in the general formula (V) are alkyl groups having an ether bond, and together form a ring containing X.
• R 6 is each independently a substituent selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms.
• a straight-chain or branched alkyl group having 1 to 12 carbon atoms a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or a straight-chain or branched alkyl group having 1 to 12 carbon atoms, which may have It is a cycloalkyl group.
• r is an integer of 1 to 5
• R 5 is each independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
• t is an integer of 1 to 6.
• B and C may be the same, but are preferably different.
• structures of the general formulas (VI), (VIII), and (IX) are preferred, in which at least one of the aromatic rings has at least one sulfonic acid group.
• the structures of the general formulas (VI) to (XIV) are the same, and only the substituents other than the sulfonic acid group are different, and at least one of the aromatic rings Also preferred are structures in which each has at least one sulfonic acid group.
• B and C are different, in general formulas (I) and (i), p is not 0, and B has a structure represented by the above general formula (IV), or the above general formula (V ), R 3 is a phenyl group or naphthyl group which may have a substituent, and R 4 is an alkyl group or an ether bond which may have a substituent.
• R 3 and R 4 may be combined with each other to form a ring containing X, and the aromatic At least one of the rings has at least one sulfonic acid group, and C is a structure in which R 3 and R 4 each independently have a substituent in the structure represented by the general formula (V).
• B is selected from the group consisting of the general formulas (VI) to (XI), and at least one of its aromatic rings has at least one sulfonic acid group
• C is a structure represented by the general formula ( More preferably, it is selected from the group consisting of XII) to (XIV). With such a structure, the amount of sulfonic acid groups introduced into the polymer compound having the structure represented by general formula (I) can be adjusted.
• the polymer compound having the structure represented by general formula (I) is preferably a compound represented by general formula (II).
• the compound represented by the general formula (II) is more preferably a compound represented by the following general formula (ii).
• rings A, B, C, n, o and p are as defined in general formula (I).
• carbon, B, C, n, o and p of ring A are as defined in general formula (I).
• m is 3 or more, preferably 3 to 100, more preferably 15 to 60.
• Ar 1 is an aromatic group having 6 to 40 carbon atoms and which may have a substituent. Note that the number of carbon atoms includes the number of carbon atoms of substituents. Examples of the aromatic group include divalent groups such as benzene, naphthalene, acetylene, biphenyl, indacene, biphenylene, acenaphthylene, acenaphthene, fluorene, phenalene, phenanthrene, tetralin, and anthracene. Examples of the substituent include the same substituents as R 1 and R 2 in the following general formula (III), each independently when there is a plurality of substituents. Ar 1 has a structure different from that represented by general formula (I). In the general formulas (II) and (ii), it is preferable that Ar 1 has a structure represented by the following general formula (III).
• R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, or an aromatic group that may have a substituent, and preferably have no substituent.
• R 1 and R 2 may be combined with each other to form a ring.
• each is preferably independently an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, and/or an alkoxy group having 1 to 3 carbon atoms.
• the ion exchange capacity (IEC (mmol/g)) of the polymer compound having the structure represented by general formulas (I) and (i) is preferably 0.1 to 6, more preferably 1 to 5, and 1.5 -4 is more preferred.
• the number of sulfonic acid groups in the polymer compound having the structure represented by general formula (I) is preferably such that the ion exchange capacity falls within the above range.
• ring A of general formulas (I) and (i) carbons other than the carbons bonded to the main chain and the carbons bonded to B and C may be substituted with halogen atoms.
• the main chain is the main chain of a polymer compound having a structure represented by general formula (I).
• the halogen atom a fluorine atom is preferred.
• the number of halogen atoms substituted in ring A is preferably 0 to 5 per ring A, more preferably 0 to 3.
• a polymer compound having a structure represented by general formulas (I) and (i) is suitably used as an electrolyte for an anode catalyst layer and/or a cathode catalyst layer of a polymer electrolyte fuel cell. Therefore, the polymer compound having the structure represented by the general formula (I) is preferably included in the catalyst layer of the polymer electrolyte fuel cell.
• the polymer electrolyte fuel cell is as described in the first aspect of the present invention.
• GPC gel permeation chromatography
• IEC ion exchange capacity
• the polymerization degree m of the polymer was calculated by the following formula using the formula weight per repeating unit and the number average molecular weight (Mn) obtained by GPC measurement.
• Degree of polymerization m (number average molecular weight (Mn)) / (molecular weight per repeating unit)
• a solution dissolved in 1.5 mL (manufactured by Kanto Kagaku Co., Ltd.) was added.
• the reaction solution was heated to 105°C and stirred for 24 hours. After cooling to room temperature, the reaction solution was added dropwise to a methanol-ion-exchanged water-35% HCl mixture and stirred. Perform vacuum filtration, dry the obtained filtrate, then dissolve it in tetrahydrofuran, and dissolve sodium N,N-diethyldithiocarbamate trihydrate (Kanto Kagaku Co., Ltd.) in methanol to a concentration of 0.32%. The solution was added dropwise to the solution and stirred.
• Tris(dibenzylideneacetone)dipalladium (0) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.0 .050 g, tris-o-methoxyphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.078 g, cesium carbonate (manufactured by Kanto Kagaku Co., Ltd.) 5.35 g, and cyclopentyl methyl ether (Kanto Kagaku Co., Ltd.) 42 mL.
• the obtained filtrate was dried, dissolved in chloroform, added dropwise to methanol, and stirred. Filtration was performed under reduced pressure, and the resulting filtrate was dried. The dried filtrate was dissolved in chloroform again, added dropwise to methanol, and stirred. Filtration under reduced pressure was performed, and the resulting filtrate was dried to obtain 0.48 g (yield: 90%) of P-4-1.
• TEC10E50E manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.
• Example 6 1.5% water/1-propanol (1 part by weight) of the electrolyte synthesized in Example 6 was used instead of the 5% water/1-propanol (1 part by weight) solution of the electrolyte described above.
• a catalyst ink was prepared in the same manner except that a solution (parts by mass/1 part by mass) was added.
• Comparative Example 1 5% Nafion dispersion (DE520 CS type, manufactured by Wako Pure Chemical Industries, Ltd.) was added instead of the 5% water/1-propanol (1 part by mass/1 part by mass) solution of the electrolyte described above.
• a catalyst ink was prepared in the same manner except for the above. I/C is the mass ratio of electrolyte to carbon.
• a gas diffusion layer with a microporous layer (SIGRACET GDL28BC, manufactured by SGL Carbon) was placed on a hot plate at 80°C, and the catalyst ink prepared by the above method was applied to the microporous layer side using a spray method, and then the catalyst ink prepared by the above method was applied onto the microporous layer.
• a gas diffusion electrode with a catalyst layer formed thereon was fabricated. Table 1 shows the amount of platinum catalyst per unit area.
• a polymer electrolyte fuel cell was fabricated by covering the membrane electrode assembly obtained above except for the electrode part with a pair of gaskets, and arranging a separator that also served as a gas flow path, a current collector plate, an insulating sheet, and a clamping plate on both sides. did. This was used as a single cell, and one side was used as an oxygen electrode to supply air, and the other side was used as a fuel electrode to supply hydrogen to generate electricity.
• the power generation conditions were as follows: cell temperature 80°C, air side and fuel side relative humidity both listed in Table 1, and each gas was supplied so that the fuel and oxygen utilization rates were 5%, and power generation performance evaluation (output voltage) was carried out. Table 1 shows the output voltage at 1.0 A/cm 2 o'clock.
• Examples 1 to 8 have higher power generation performance than Comparative Example 1, which is a conventional fluorine-based ionomer, because the output voltage at a current density of 1.0 A/cm 2 is higher than that of Comparative Example 1. was confirmed. It is presumed that in the present invention, by using a polymer compound having a bulky structure introduced into the side chain, the gas diffusivity of the catalyst layer was improved and good power generation characteristics were exhibited.
• the catalyst composition according to the first aspect and the compound according to the second aspect of the present invention have excellent power generation properties and are therefore suitably used in the catalyst layer of polymer electrolyte fuel cells.

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