JP2008226835A - ポリ電解質膜のフッ素処理 - Google Patents
ポリ電解質膜のフッ素処理 Download PDFInfo
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- JP2008226835A JP2008226835A JP2008034654A JP2008034654A JP2008226835A JP 2008226835 A JP2008226835 A JP 2008226835A JP 2008034654 A JP2008034654 A JP 2008034654A JP 2008034654 A JP2008034654 A JP 2008034654A JP 2008226835 A JP2008226835 A JP 2008226835A
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- 239000012528 membrane Substances 0.000 title claims abstract description 89
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011737 fluorine Substances 0.000 title claims abstract description 40
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 40
- 229920000867 polyelectrolyte Polymers 0.000 title description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims abstract description 48
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 48
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 46
- 239000000446 fuel Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- -1 thioether ketone Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229920000412 polyarylene Polymers 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 235000019407 octafluorocyclobutane Nutrition 0.000 claims description 4
- PBGVMIDTGGTBFS-UHFFFAOYSA-N but-3-enylbenzene Chemical compound C=CCCC1=CC=CC=C1 PBGVMIDTGGTBFS-UHFFFAOYSA-N 0.000 claims description 3
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims 2
- 229920005597 polymer membrane Polymers 0.000 abstract description 8
- 238000007865 diluting Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 13
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 229920000557 Nafion® Polymers 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 2
- 239000012809 cooling fluid Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- 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
- C08J5/2287—After-treatment
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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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Abstract
【解決手段】炭化水素ポリマー膜をフッ素で処理してその酸性度及び酸含量を増加させることを含む。フッ素ガスを不活性ガスで希釈した混合ガスを、炭化水素膜が配置されている反応容器62に導入して、フッ素を膜上に堆積させる。ガスは、フッ素が膜を燃焼しないように十分に遅い速度で容器中に導入する。
【選択図】図2
Description
本発明の教示によれば、炭化水素ポリマー膜をフッ素で処理して、その酸含量を増加させて、部分的にフッ素化されているか又はペルフッ素化されている炭化水素膜を生成することを含む、燃料電池用のポリマー電解質膜を提供する方法が開示される。フッ素ガスは、不活性ガスと混合してフッ素を希釈して、炭化水素膜を燃焼しないようにする。混合ガスを、炭化水素膜が配置されている容器中に導入し、膜をフッ素に曝露するか、或いはフッ素と接触させる。ガスは、フッ素によって膜が燃焼しないように十分に遅い速度で容器中に導入する。
各態様の詳細な説明
炭化水素膜上にフッ素を堆積させて、燃料電池用の高酸性ポリマー電解質膜を与えるシステム及び方法に関する本発明の各態様の以下の説明は、事実上単に例示に過ぎず、いかなるようにも本発明又はその適用又は使用を限定するものではない。
フッ素で処理してその酸性度をペルフルオロスルホン酸膜と同等のレベルに増加させることができる多くの好適な炭化水素ポリマー膜が入手可能である。好適な試料としては以下のものが挙げられるが、これらに限定されない。
F2処理Nafion DE−0838WX;
Nafion 112;
F2処理Nafion 112;
F2処理溶液キャストNafion 1000;
F2処理ポリ[ペルフルオロシクロブタン](PFCB);
F2処理PFCB(30分間);
F2処理PFCB(室温で1時間);
F2処理スルホン化ポリ[ビフェニル−ペルフルオロシクロブタン];
Parmax 1200(Mississippi Polymer Technologyからのポリフェニレン);
F2処理Parmax 1200;
樹脂1gあたり1.0〜3ミリ当量のスルホン酸のイオン交換容量を有するスルホン化Parmax 1200;
F2処理スルホン化Parmax 1200(30分間及び1時間);
ポリアリーレンチオエーテル;
polyMaterials,AG,Kaufbeuren,Germanyから入手できるSV359−PD356aと名付けられたスルホン化ポリアリーレンエーテルケトン;
F2処理SV359−PD356a;
SV359−PD356b(polyMaterials,AG,Kaufbeuren,Germanyから入手できるスルホン化ポリアリーレンエーテルケトン);
BS46−PD3726−009(polyMaterials,AG,Kaufbeuren,Germanyから入手できるスルホン化ポリアリーレンチオエーテルケトン);
スルホン化ポリアリーレンチオエーテルスルホン;
スルホン化ポリ(4−フェニル−1−ブテン)、又は、ポリスチレンのような他の脂肪族−芳香族ポリマー;
F2処理BS46−PD3726−009。
Claims (23)
- 炭化水素膜を提供し;そして
炭化水素膜の酸含量が増加するように炭化水素膜上にフッ素を堆積させる;
ことを含む、燃料電池用のポリマー電解質膜を提供する方法。 - 炭化水素膜を提供することが、芳香族スルホン酸膜を提供することを含む、請求項1に記載の方法。
- 炭化水素膜を提供することが、直鎖炭化水素膜を提供することを含む、請求項1に記載の方法。
- 直鎖炭化水素膜を提供することが、脂肪族スルホン酸膜を提供することを含む、請求項3に記載の方法。
- 直鎖炭化水素膜を提供することが、脂肪族−芳香族スルホン酸膜を提供することを含む、請求項3に記載の方法。
- 膜上にフッ素を堆積させることが、膜上に、不活性ガスと混合したフッ素ガスを堆積させることを含む、請求項1に記載の方法。
- ガス中のフッ素の割合が20重量%未満である、請求項6に記載の方法。
- 不活性ガスが窒素である、請求項6に記載の方法。
- ガスを、ガスが膜を燃焼しないように十分に遅い速度で、炭化水素膜が配置されている容器中に導入する、請求項6に記載の方法。
- 混合ガス中のフッ素の濃度が、膜を燃焼させないような十分に低いものである、請求項6に記載の方法。
- 膜上にフッ素を堆積させることが、膜上にフッ素化溶媒を堆積させることを含む、請求項1に記載の方法。
- フッ素化溶媒がFreonである、請求項11に記載の方法。
- 炭化水素膜を提供することが、ペルフルオロシクロブタン、Parmax、ポリアリーレンチオエーテルケトン、ポリアリーレンエーテルチオスルホン、ポリ(4−フェニル−1−ブテン)、及びポリアリーレンエーテルケトン膜からなる群から選択されるスルホン化炭化水素膜を提供することを含む、請求項1に記載の方法。
- 反応容器内に炭化水素膜を提供し;
フッ素ガス及び不活性ガスを含む混合ガスを提供し;そして
反応容器中に混合ガスを導入して、膜の酸含量が向上するように混合ガスを膜上に堆積させる;
ことを含む、燃料電池用のポリマー電解質膜を提供する方法。 - 炭化水素膜を提供することが、芳香族スルホン酸膜を提供することを含む、請求項14に記載の方法。
- 炭化水素膜を提供することが、直鎖炭化水素膜を提供することを含む、請求項14に記載の方法。
- 混合ガス中のフッ素の割合が20重量%未満である。請求項14に記載の方法。
- 不活性ガスが窒素である、請求項14に記載の方法。
- 混合ガス中のフッ素の濃度が、膜を燃焼しないような十分に低いものである、請求項14に記載の方法。
- 混合ガスを、混合ガスが膜を燃焼しないように十分に遅い速度で反応容器中に導入する、請求項14に記載の方法。
- 炭化水素膜を提供することが、ペルフルオロシクロブタン、Parmax、ポリアリーレンチオエーテルケトン、ポリアリーレンエーテルチオスルホン、ポリ(4−フェニル−1−ブテン)、及びポリアリーレンエーテルケトン膜からなる群から選択されるスルホン化炭化水素膜を提供することを含む、請求項14に記載の方法。
- 炭化水素基層;及び
炭化水素基層の酸含量が増加するように炭化水素基層上に堆積されたフッ素層;
を含む、燃料電池用のポリマー電解質膜。 - 炭化水素基層が、芳香族スルホン酸層及び直鎖炭化水素層からなる群から選択される、請求項22に記載の膜。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US11/676,449 US20080199753A1 (en) | 2007-02-19 | 2007-02-19 | Fluorine Treatment of Polyelectrolyte Membranes |
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JP2008226835A true JP2008226835A (ja) | 2008-09-25 |
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JP2008034654A Pending JP2008226835A (ja) | 2007-02-19 | 2008-02-15 | ポリ電解質膜のフッ素処理 |
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US (1) | US20080199753A1 (ja) |
JP (1) | JP2008226835A (ja) |
CN (1) | CN101252197A (ja) |
DE (1) | DE102008009114A1 (ja) |
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US20090163692A1 (en) * | 2007-12-21 | 2009-06-25 | General Electric Company | Aromatic polyethers |
US8354201B2 (en) * | 2009-08-28 | 2013-01-15 | GM Global Technology Operations LLC | Fuel cell with spatially non-homogeneous ionic membrane |
CN101691423B (zh) * | 2009-09-18 | 2011-06-08 | 中山大学 | 一种氟化改性磺化聚芳醚及其制备方法和应用 |
US9517523B2 (en) * | 2010-04-09 | 2016-12-13 | Illinois Tool Works Inc. | System and method of reducing diffusible hydrogen in weld metal |
US9764409B2 (en) | 2011-04-04 | 2017-09-19 | Illinois Tool Works Inc. | Systems and methods for using fluorine-containing gas for submerged arc welding |
US9821402B2 (en) | 2012-03-27 | 2017-11-21 | Illinois Tool Works Inc. | System and method for submerged arc welding |
US20140080080A1 (en) * | 2012-09-14 | 2014-03-20 | GM Global Technology Operations LLC | Annealed WVT Membranes to Impart Durability and Performance |
US8906572B2 (en) | 2012-11-30 | 2014-12-09 | General Electric Company | Polymer-electrolyte membrane, electrochemical fuel cell, and related method |
CN103746123B (zh) * | 2014-02-18 | 2016-08-31 | 武汉理工大学 | 质子交换膜燃料电池金属双极板及其构成的电堆 |
CN109904499A (zh) * | 2017-12-07 | 2019-06-18 | 大连融科储能技术发展有限公司 | 一种含氟离子交换膜及其制备方法 |
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JP2004083864A (ja) * | 2002-06-25 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | フッ素化プロトン伝導性高分子膜およびその製造方法 |
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WO2006051748A1 (ja) * | 2004-11-10 | 2006-05-18 | Toyo Boseki Kabushiki Kaisha | プロトン伝導性ポリマー組成物およびその製造方法、該プロトン伝導性ポリマー組成物を含む触媒インク、該触媒インクを含む燃料電池 |
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JP2004083864A (ja) * | 2002-06-25 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | フッ素化プロトン伝導性高分子膜およびその製造方法 |
JP2004083663A (ja) * | 2002-08-23 | 2004-03-18 | Toyota Central Res & Dev Lab Inc | 高耐久高分子電解質及びその製造方法 |
JP2005048121A (ja) * | 2003-07-31 | 2005-02-24 | Asahi Kasei Corp | パーフルオロスルホン酸ポリマー |
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JP2020194779A (ja) * | 2016-03-31 | 2020-12-03 | コーロン インダストリーズ インク | イオン交換膜、この製造方法、及びこれを含むエネルギー貯蔵装置 |
JP7022178B2 (ja) | 2016-03-31 | 2022-02-17 | コーロン インダストリーズ インク | イオン交換膜、この製造方法、及びこれを含むエネルギー貯蔵装置 |
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CN101252197A (zh) | 2008-08-27 |
US20080199753A1 (en) | 2008-08-21 |
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