JP4959115B2 - プロトン伝導性電解質及び燃料電池 - Google Patents
プロトン伝導性電解質及び燃料電池 Download PDFInfo
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- JP4959115B2 JP4959115B2 JP2004059139A JP2004059139A JP4959115B2 JP 4959115 B2 JP4959115 B2 JP 4959115B2 JP 2004059139 A JP2004059139 A JP 2004059139A JP 2004059139 A JP2004059139 A JP 2004059139A JP 4959115 B2 JP4959115 B2 JP 4959115B2
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- acid
- polyamide
- sulfamic acid
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- fuel cell
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- 239000000446 fuel Substances 0.000 title claims description 23
- 239000012078 proton-conducting electrolyte Substances 0.000 title claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 33
- 229920002647 polyamide Polymers 0.000 claims description 33
- 239000003792 electrolyte Substances 0.000 claims description 31
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 16
- 229920005575 poly(amic acid) Polymers 0.000 claims description 13
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 12
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 6
- DQMFXGQHSPWNOA-UHFFFAOYSA-N triethylazanium;sulfamate Chemical compound NS([O-])(=O)=O.CC[NH+](CC)CC DQMFXGQHSPWNOA-UHFFFAOYSA-N 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Chemical group 0.000 claims description 3
- 239000004305 biphenyl Chemical group 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical group C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000002253 acid Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Natural products CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 3
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- 229920003934 Aciplex® Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MYMDOKBFMTVEGE-UHFFFAOYSA-N methylsulfamic acid Chemical compound CNS(O)(=O)=O MYMDOKBFMTVEGE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- H01M8/103—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]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyamides (AREA)
Description
フッ素を含有しない電解質としては、水処理用イオン交換樹脂やイオン交換膜等としてポリスチレンスルホン酸、燃料電池用としてスルホン酸化芳香族ポリマー等が提案されている(特許文献1、非特許文献1等)。しかしながら、これらは、耐熱性や化学的安定性が燃料電池用電解質として実用化するには不充分である。
「プロトン伝導性電解質」
本発明のプロトン伝導性電解質は、ポリアミド主鎖に、側鎖としてスルファミド酸基が導入されたポリアミドスルファミド酸を1種又は2種以上含むことを特徴とする。
上記ポリアミドスルファミド酸は、側鎖に導入された酸性度の高いスルファミド酸基によってプロトンを効率良く生成すると同時にこれを伝導する。これによって高いプロトン伝導性を呈するものである。
(i)N,N’−ジメチルアセトアミド、N,N’−ジメチルホルムアミド、N−メチルピロリジン、ジメチルスルホキシド等に可溶で、水、メタノール、クロロホルム、ヘキサン、ベンゼン、トルエン等に不溶であること、
(ii)高い耐熱性を呈すること(熱重量分析結果参照)、
(iii)キャスト法にて成膜することで、均質でかつ強靭な膜が得られること、
を確認している(詳細については「実施例」の項参照)。
例えば、得られる膜の強度を高めるために、補強剤としてポリテトラフルオロエチレン等の含フッ素ポリマーを併用することができる。
その他、塩基性を示す含窒素ポリマー、含酸素ポリマー、含硫黄ポリマー等を併用し、イオンコンプレックス電解質として用いることもできる。
また、オルト燐酸、メタ燐酸、ポリ燐酸等を併用し、ゲル状電解質とすることもできる。
上記の本発明のプロトン伝導性電解質を用いることで、本発明の燃料電池を提供することができる。
本発明の燃料電池は、一対の電極と、これら電極間に配置された電解質膜とを具備してなり、電解質膜及び/又は少なくとも一方の電極に、上記の本発明のプロトン伝導性電解質が用いられていることを特徴とする。
電極への適用例については「実施例」の項において挙げる。
「ポリアミドスルファミド酸の合成」
ポリアミド酸(3)として、Ar1:ベンゼン、Ar2:ベンゼン、平均分子量4.1×1.04のものを用い、[化3]に示した合成スキームにて、ポリアミドスルファミド酸を合成した。
別途、ジクロロメタン3mlにアミド硫酸0.49g(5mmol)及びトリエチルアミン0.51g(5mmol)を添加し、アミド硫酸トリエチルアミン塩を生成し、これを、上記ポリマー溶液に窒素雰囲気下徐々に滴下して3時間攪拌混合した。反応溶液を400mlジクロロメタン中に注入して沈殿物をろ別し、ジクロロメタンで洗浄後、50℃で一昼夜加熱減圧乾燥し、黄色粉末0.32gを得た(収率81%)。
上記で得たポリアミドスルファミド酸のN,N’−ジメチルアセトアミド溶液に、白金を50質量%担持するカーボン粉末を加え、十分攪拌して懸濁液を得た。なお、固形分基準で、白金担持カーボン粉末とポリマーとの質量比が2:1になるように調整した。この懸濁液を表面細孔径が0.1〜10μm、厚みが40μmの多孔質カーボン層を形成したカーボン多孔質体(気孔率75%)上にダイコーターにて塗布し、これを乾燥して燃料電池用の多孔質電極とした。
この電極を一対作製して、上記で得たポリアミドスルファミド酸膜を挟み燃料電池単セルとした。燃料として加湿水素、酸化剤として加湿空気をそれぞれ供給し、80℃にて発電試験を行ったところ、開路電圧0.95V、200mA/cm2の電流密度の条件において、0.65Vの電圧が得られ、良好な燃料電池特性を呈した。
原料のポリアミド酸の平均分子量を1.1×1.05とした以外は実施例1と同様にして、ポリアミドスルファミド酸を得た(通算収率71%)。
得られたポリアミドスルファミド酸の特性を以下に示す。
(a)1H−NMRスペクトル(DMSO−d6,500MHz):7.02−7.14(m,4H),7.51−7.68(m,4H),7.70−7.84(m,1H),7.95−8.25(m,1H),10.43−10.65(m,2H)
(b)IRスペクトルにおけるカルボニル基由来の吸収:1685,1655cm−1(vC=O)、スルホン酸基由来の吸収:1116,1051cm−1(vS=O)
(c)平均分子量:1.5×105(GPC測定、ポリスチレン換算、溶離液:N,N’−ジメチルホルムアミド)
(d)10%熱分解温度(Td10%):277℃
(e)イオン交換容量:2.9 meq g−1(計算値3.5 meq g−1)
(f)プロトン伝導度:9.1×10−4 Scm−1オーダー(80℃,湿度100%)
ポリアミド酸(3)中のAr1をナフタレンとした以外は実施例1と同様にして、ポリアミドスルファミド酸を得た(通算収率76%)。
得られたポリアミドスルファミド酸の特性を以下に示す。
(a)1H−NMRスペクトル(DMSO−d6,500MHz):7.04−7.18(m,4H),7.53−7.72(m,4H),8.20−8.25(m,2H),8.51−8.68(m,2H),10.39−10.60(m,2H)
(b)IRスペクトルにおけるカルボニル基由来の吸収:1684,1655cm−1(vC=O)、スルホン酸基由来の吸収:1116,1051cm−1(vS=O)
(c)平均分子量:6.6×104(GPC測定、ポリスチレン換算、溶離液:N,N’−ジメチルホルムアミド)
(d)10%熱分解温度(Td10%):331℃
(e)イオン交換容量:2.6 meq g−1(計算値3.0 meq g−1)
(f)プロトン伝導度:6.7×10−4 Scm−1オーダー(80℃,湿度100%)
Claims (4)
- 前記ポリアミドスルファミド酸が、ポリアミド酸の側鎖カルボン酸基のスルファミド化物であることを特徴とする請求項1に記載のプロトン伝導性電解質。
- 前記ポリアミドスルファミド酸が、ポリアミド酸の側鎖カルボン酸基を酸クロライド化後、アミド硫酸トリエチルアミン塩と反応させ、さらに陽イオン交換して得られるものであることを特徴とする請求項2に記載のプロトン伝導性電解質。
- 一対の電極と、これら電極間に配置された電解質膜とを具備してなり、
前記電解質膜及び/又は少なくとも一方の前記電極に、請求項1〜3のいずれかに記載のプロトン伝導性電解質が用いられていることを特徴とする燃料電池。
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JP4593420B2 (ja) * | 2005-09-27 | 2010-12-08 | 三星エスディアイ株式会社 | 燃料電池用のプロトン伝導性電解質及び燃料電池用プロトン伝導性電解質の製造方法並びに燃料電池 |
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