JP6154035B2 - 高分子電解質膜の製造方法 - Google Patents
高分子電解質膜の製造方法 Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims description 57
- 239000005518 polymer electrolyte Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000004020 conductor Substances 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000010416 ion conductor Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 14
- 239000010954 inorganic particle Substances 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000002612 dispersion medium Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 description 26
- 229920001721 polyimide Polymers 0.000 description 26
- 239000000446 fuel Substances 0.000 description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
- 239000003792 electrolyte Substances 0.000 description 24
- 238000009987 spinning Methods 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 13
- 239000000835 fiber Substances 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000001523 electrospinning Methods 0.000 description 10
- -1 hydrogen ions Chemical class 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 9
- 229920005575 poly(amic acid) Polymers 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- JUNAPQMUUHSYOV-UHFFFAOYSA-N 2-(2h-tetrazol-5-yl)acetic acid Chemical compound OC(=O)CC=1N=NNN=1 JUNAPQMUUHSYOV-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
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- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 229920002492 poly(sulfone) Polymers 0.000 description 4
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- 238000010248 power generation Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 230000008018 melting Effects 0.000 description 3
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- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002577 polybenzoxazole Polymers 0.000 description 2
- 230000007723 transport mechanism Effects 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
Classifications
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1065—Polymeric electrolyte materials characterised by the form, e.g. perforated or wave-shaped
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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
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
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- H01M8/00—Fuel cells; Manufacture thereof
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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
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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
- H01M8/1023—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
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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
- 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
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- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
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- H—ELECTRICITY
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1055—Inorganic layers on the polymer electrolytes, e.g. inorganic coatings
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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- 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
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- H01M2300/0091—Composites in the form of mixtures
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- 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
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- 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
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- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Nonwoven Fabrics (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Artificial Filaments (AREA)
Description
本発明によると、前記アゾール環が接合された無機粒子が、多孔性支持体を構成する繊維の表面上に又は繊維の内部に存在することによって、多孔性支持体が水素イオン伝導のための媒介体としての役割をすることができる。したがって、本発明の電解質膜は、100℃以上の高温下で水分が蒸発する場合にも、又は50%以下の低湿条件下でも優れた水素イオン伝導性を示すことができる。
1H―テトラゾール―5―酢酸(>99.9%)(Aldrich Chemical)1gをエタノール50mLに1時間溶解させた。シリカナノ粒子(Cabot Corporation)1gをエタノール50mLに入れた後、常温で超音波粉砕機で1時間分散させた。続いて、エタノールに溶けているテトラゾール酢酸溶液をシリカナノ粒子が分散されている溶液に投与し、常温で3時間撹拌させた。続いて、60℃の真空オーブンで24時間乾燥させて溶媒を除去した後、シリカナノ粒子とテトラゾール酢酸の重さの割合が1:1である自己陽性子伝導性物質を製造した。
15重量%のポリアミック酸をテトラヒドロフラン(THF)紡糸溶媒に溶かして製造した紡糸ドープを25℃の温度及び30kVの電圧が印加された状態で電気紡糸してポリイミド前駆体ナノウェブを形成した後、350℃のオーブンで5時間熱処理してポリイミドナノウェブを製造した。
15重量%のポリビニルアルコール1gを10gの水に溶解させた後、自己陽性子伝導性物質を分散させることによって分散液を製造し、前記分散液10gをポリイミドナノウェブに加えたことを除いては、実施例1と同一の方法で高分子電解質膜を完成した。
15重量%のポリアミック酸をテトラヒドロフラン(THF)紡糸溶媒に溶かした後、10gの自己陽性子伝導性物質を添加することによって製造された紡糸ドープを25℃の温度及び30kVの電圧が印加された状態で電気紡糸してポリイミド前駆体ナノウェブを形成した後、350℃のオーブンで5時間熱処理してポリイミドナノウェブを製造した。
15重量%のポリアミック酸と共に、15重量%のポリビニルアルコール10gをテトラヒドロフラン(THF)紡糸溶媒に溶かした後、10gの自己陽性子伝導性物質を添加することによって紡糸ドープを製造したことを除いては、実施例3と同一の方法で高分子電解質膜を完成した。
15重量%のポリアミック酸をテトラヒドロフラン(THF)紡糸溶媒に溶かして製造した紡糸ドープを25℃の温度及び30kVの電圧が印加された状態で電気紡糸してポリイミド前駆体ナノウェブを形成した後、350℃のオーブンで5時間熱処理してポリイミドナノウェブを製造した。続いて、N―メチル―2―ピロリドン(NMP)にスルホン化ポリスルホンを溶解させて製造した10重量%のイオン伝導体溶液に、前記ポリイミドナノウェブを常温で20分間3回ディッピングし、このとき、微細気泡の除去のために減圧雰囲気を1時間にわたって適用した。その後、120℃に維持された熱風オーブンで3時間乾燥させてNMPを除去し、高分子電解質膜を完成した。
15重量%のポリアミック酸と共に、15重量%のポリビニルアルコール10gをテトラヒドロフラン(THF)紡糸溶媒に溶かして紡糸ドープを製造したことを除いては、比較例1と同一の方法で高分子電解質膜を完成した。
実施例及び比較例によって製造された電解質膜のコンダクタンスを定電流4端子法によって測定した。具体的には、1*3cm2の矩形状にサンプリングされた電解質膜を蒸留水に浸漬した状態の100%相対湿度条件で20分ないし30分安定化させた後、一定の交流電流を電解質膜の両端に印加しながら中央で発生する交流電位差を測定し、水素イオン伝導性を得た。続いて、前記相対湿度を80%、60%、40%、及び20%にそれぞれ変更させながら、同一の方法で水素イオン伝導性を測定した。このとき、水素イオン伝導性測定装置としては、試料の厚さ方向での伝導度を測定できるスルー―プレーンメンブレンテストシステム(Thgrough―Plane Membrane Test System)(Scribner Associates社、MTS 740)を用いた。その結果は、下記の表1に示す通りである。
Claims (3)
- 炭化水素含有高分子によって形成された多孔性支持体を準備する工程、
多孔性支持体にプロトン伝導性物質を分散させる工程及び
多孔性支持体にスルホン酸基を有する炭化水素含有高分子からなるイオン伝導体を含浸させる工程を含み、
前記プロトン伝導性物質は、ピラゾール、イミダゾール、トリアゾール又はテトラゾールで官能化された、シリコン酸化物、金属酸化物又はアルカリ土類金属酸化物からなる無機粒子を含むことを特徴とする高分子電解質膜の製造方法。 - 前記多孔性支持体を準備する工程は、不織布を形成する工程であり、
前記多孔性支持体にプロトン伝導性物質を分散させる工程は、前記プロトン伝導性物質が分散されている分散液を前記不織布上にコーティングする工程である請求項1に記載の高分子電解質膜の製造方法。 - 前記分散液の分散媒には親水性基を有する高分子が溶解されている請求項2に記載の高分子電解質膜の製造方法。
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