JP6548176B2 - ポリフェニルスルホン系プロトン伝導性高分子電解質、プロトン伝導性固体高分子電解質膜、固体高分子形燃料電池用の電極触媒層及びその製造方法、並びに燃料電池 - Google Patents
ポリフェニルスルホン系プロトン伝導性高分子電解質、プロトン伝導性固体高分子電解質膜、固体高分子形燃料電池用の電極触媒層及びその製造方法、並びに燃料電池 Download PDFInfo
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- JP6548176B2 JP6548176B2 JP2017535314A JP2017535314A JP6548176B2 JP 6548176 B2 JP6548176 B2 JP 6548176B2 JP 2017535314 A JP2017535314 A JP 2017535314A JP 2017535314 A JP2017535314 A JP 2017535314A JP 6548176 B2 JP6548176 B2 JP 6548176B2
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- polymer electrolyte
- proton conducting
- fuel cell
- solid polymer
- proton
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- 239000012528 membrane Substances 0.000 title claims description 51
- 239000005518 polymer electrolyte Substances 0.000 title claims description 35
- 239000003054 catalyst Substances 0.000 title claims description 25
- 239000007787 solid Substances 0.000 title claims description 23
- 239000000446 fuel Substances 0.000 title claims description 18
- 229920001940 conductive polymer Polymers 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920000491 Polyphenylsulfone Polymers 0.000 title description 44
- 229920000642 polymer Polymers 0.000 title description 15
- 239000003792 electrolyte Substances 0.000 claims description 30
- 238000004132 cross linking Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 26
- 125000001174 sulfone group Chemical group 0.000 claims description 24
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
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- 238000011282 treatment Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229920000867 polyelectrolyte Polymers 0.000 claims description 10
- 239000002322 conducting polymer Substances 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 230000005670 electromagnetic radiation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000012078 proton-conducting electrolyte Substances 0.000 claims 1
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- 238000006243 chemical reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 229920000557 Nafion® Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 8
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- 229920000554 ionomer Polymers 0.000 description 7
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
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- 238000005227 gel permeation chromatography Methods 0.000 description 6
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 perfluoro groups Chemical group 0.000 description 5
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- 150000002500 ions Chemical class 0.000 description 3
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- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- TUFKHKZLBZWCAW-UHFFFAOYSA-N 2-(1-ethenoxypropan-2-yloxy)ethanesulfonyl fluoride Chemical compound C=COCC(C)OCCS(F)(=O)=O TUFKHKZLBZWCAW-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L81/08—Polysulfonates
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- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R33/00—Arrangements or instruments for measuring magnetic variables
- G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
- G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
- G01R33/46—NMR spectroscopy
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- H01M2300/0065—Solid electrolytes
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- 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
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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Description
なお、ここでのスルホン化は、スルホン基(−SO3H)を有する場合のみならず、そのアルカリ金属(例えばNa)塩又はアルカリ土類金属塩である基を有する場合も包含する。
また、前記スルホン化ポリフェニル化合物は、以下のモノマーから選択される少なくとも1種から形成された重合体もしくは共重合体を骨格構造とするか、または、以下の重合体もしくは共重合体から選択される少なくとも1種を骨格構造としてよい。
ここで、前記架橋は、熱処理、架橋剤を添加することによる架橋化処理、及び、放射線または電磁波照射処理からなる群から選択された一の処理または複数の処理の組み合わせによって行ってよい。
また、前記架橋剤は、多価アルコールであってよい。
ここで、前記架橋は、熱処理、架橋剤を添加することによる架橋化処理、及び、放射線または電磁波照射処理からなる群から選択された一の処理または複数の処理の組み合わせによって行ってよい。
スルホン化ポリフェニル化合物は、1つの繰り返しユニットあたり平均2個またはさらに多くのスルホン基を有すること以外は、スルホン化の程度及び位置ならびに重合の程度について特に限定されない。1つの繰り返しユニットが有するスルホン基の平均数は、通常、2個以上16個以下であってよく、プロトン伝導度及び機械的強度のバランスを考慮すれば、2個以上8個以下がより好ましい。典型的には、1つの繰り返しユニットが有するスルホン基の平均数は、2個、4個又は6個であってよい。
スルホン基の導入方法は、特に限定されず、公知のいずれの方法に依ってもよい。スルホン化ポリフェニルスルホン(SPPSU)に関する限りでは、例えば、特開2015−170583号公報(国立研究開発法人物質・材料研究機構)の実施例に開示されている方法を用いることができる。具体的に、一繰り返し単位あたり2個のスルホン基が導入されたスルホン化ポリフェニルスルホンである2S−PPSUおよび一繰り返し単位あたり4個のスルホン基が導入されたスルホン化ポリフェニルスルホンである4S−PPSUの合成については、後の実施例において詳述する。
なお、式中のn(繰り返し単位の数)は、特に限定されるものではないが、例えば、ポリフェニル化合物の重量平均分子量MW(ゲルパーミエーションクロマトグラフィー法により測定されるポリスチレン換算の重量平均分子量)が5,000〜500,000の範囲内になるようなnであり、好ましくは10,000〜400,000、より好ましくは50,000〜350,000の範囲内になるようなnである。また、別の実施形態において、式中のn(繰り返し単位の数)は、特に限定されるものではないが、例えば、ポリフェニル化合物の数平均分子量Mn(ゲルパーミエーションクロマトグラフィー法により測定されるポリスチレン換算の数平均分子量)が4,000〜400,000の範囲内になるようなnであり、好ましくは10,000〜300,000、より好ましくは50,000〜250,000の範囲内になるようなnである。
なお、式中のn(繰り返し単位の数)は、特に限定されるものではないが、例えば、ポリフェニル化合物の重量平均分子量MW(ゲルパーミエーションクロマトグラフィー法により測定されるポリスチレン換算の重量平均分子量)が5,000〜500,000の範囲内になるようなnであり、好ましくは10,000〜400,000、より好ましくは50,000〜350,000の範囲内になるようなnである。また、別の実施形態において、式中のn(繰り返し単位の数)は、特に限定されるものではないが、例えば、ポリフェニル化合物の数平均分子量Mn(ゲルパーミエーションクロマトグラフィー法により測定されるポリスチレン換算の数平均分子量)が4,000〜400,000の範囲内になるようなnであり、好ましくは10,000〜300,000、より好ましくは50,000〜250,000の範囲内になるようなnである。
また、上述した固体高分子電解質を、PEMFC用の電極触媒層に含有させるアイオノマーとして使用することもできる。このような電極触媒層は、例えば、電極触媒その他の電極触媒層に必要とされる材料と架橋前の上述した固体高分子電解質とをよく混合し、所要の形状としてから電解質を架橋させることにより製造することができる。架橋反応を起こすための手法としては、加熱による架橋では例えば180℃で所定時間保持する等、固体高分子電解質膜の製造に関して上で説明した各種の手法を、同様に使用することができる。
下式に示す反応により、繰り返しユニットにスルホン基が2個及び4個導入された化合物2S−PPSU(2スルホン化ポリフェニルスルホン)及び4S−PPSU(4スルホン化ポリフェニルスルホン)を合成した。
は、以下のようにして行った。
は、以下のようにして行った。
は、以下のようにして行った。
を、以下のようにして行った。
これらの化合物合成の最終段階で上述したように膜状にして乾燥させることで、これらの化合物の膜が得られた。これらの膜を120℃で24時間、160℃で24時間、さらに180℃で6時間処理することで、熱架橋された膜を得た。この熱処理前の膜は水に可溶であったが、熱架橋済みの膜は180℃でも水に溶解しなかった。熱架橋された2S−PPSU膜の外観を図6に示す。なお、180℃での処理時間は6時間以上であればよく、例えば24時間行ってもよい。SFPSから出発し、2S−PPSUを経てC2S−PPSU(熱架橋された2S−PPSU)を得る反応の過程は、以下のように表すことができる。
なお、ここでのプロトン伝導度は、膜抵抗測定システムMTS740(株式会社東陽テクニカ製)を用い、セル温度40、60、80、100、120℃にて相対湿度(RH)20%〜90%で測定した。インピーダンス測定では、1Hz〜1MHzの周波数範囲及び10mVのピークーピーク電圧を使用した。
Claims (10)
- スルホン基を介して架橋された膜状のプロトン伝導性高分子電解質からなるプロトン伝導性固体高分子電解質膜であって、
このプロトン伝導性高分子電解質が、
複数の繰り返しユニットを有するスルホン化ポリフェニル化合物からなるプロトン伝導性高分子電解質であって、1つの繰り返しユニットに平均2個またはさらに多くのスルホン基が導入されており、
前記スルホン化ポリフェニル化合物が以下の群から選択される、プロトン伝導性高分子電解質である、
上記プロトン伝導性固体高分子電解質膜。
- 請求項1に記載のプロトン伝導性固体高分子電解質膜を製造する方法であって、
プロトン伝導性高分子電解質を膜状に形成し、スルホン基を介して架橋することを含む、プロトン伝導性固体高分子電解質膜の製造方法。 - 前記架橋が、熱処理、架橋剤を添加することによる架橋化処理、及び、放射線または電磁波照射処理からなる群から選択された一の処理または複数の処理の組み合わせによって行われる、請求項2に記載のプロトン伝導性固体高分子電解質膜の製造方法。
- 前記架橋剤が多価アルコールである、請求項3に記載のプロトン伝導性固体高分子電解質膜の製造方法。
- 請求項1に記載のプロトン伝導性固体高分子電解質膜を含む固体高分子形燃料電池。
- スルホン基を介して架橋されたプロトン伝導性高分子電解質を含む、固体高分子形燃料電池用の電極触媒層であって、
このプロトン伝導性高分子電解質が、
複数の繰り返しユニットを有するスルホン化ポリフェニル化合物からなるプロトン伝導性高分子電解質であって、1つの繰り返しユニットに平均2個またはさらに多くのスルホン基が導入されており、
前記スルホン化ポリフェニル化合物が以下の群から選択される、プロトン伝導性高分子電解質である、
上記電極触媒層。
- 少なくとも電極触媒及びプロトン伝導性電解質を混合した後、スルホン基を介して前記プロトン伝導性電解質を架橋させる、請求項6に記載の固体高分子形燃料電池用の電極触媒層の製造方法。
- 前記架橋が、熱処理、架橋剤を添加することによる架橋化処理、及び、放射線または電磁波照射処理からなる群から選択された一の処理または複数の処理の組み合わせによって行われる、請求項7に記載の電極触媒層の製造方法。
- 請求項6に記載の電極触媒層を含む固体高分子形燃料電池。
- 複数の繰り返しユニットを有するスルホン化ポリフェニル化合物からなるプロトン伝導性高分子電解質であって、1つの繰り返しユニットに平均2個またはさらに多くのスルホン基が導入されており、
前記スルホン化ポリフェニル化合物が以下の群から選択される、プロトン伝導性高分子電解質。
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