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
- Publication number
- JP6154035B2 JP6154035B2 JP2016006223A JP2016006223A JP6154035B2 JP 6154035 B2 JP6154035 B2 JP 6154035B2 JP 2016006223 A JP2016006223 A JP 2016006223A JP 2016006223 A JP2016006223 A JP 2016006223A JP 6154035 B2 JP6154035 B2 JP 6154035B2
- Authority
- JP
- Japan
- Prior art keywords
- porous support
- electrolyte membrane
- conductive material
- polymer
- polymer electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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
- 238000005259 measurement Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 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
- 238000005470 impregnation Methods 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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
-
- 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
- H01M8/1065—Polymeric electrolyte materials characterised by the form, e.g. perforated or wave-shaped
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- 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
-
- 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
-
- 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1055—Inorganic layers on the polymer electrolytes, e.g. inorganic coatings
-
- 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
- H01M8/1058—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
-
- 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
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Artificial Filaments (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Nonwoven Fabrics (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。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020110075531A KR101767370B1 (ko) | 2011-07-29 | 2011-07-29 | 연료전지용 고분자 전해질막 및 그 제조방법 |
KR10-2011-0075531 | 2011-07-29 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014521575A Division JP5899317B2 (ja) | 2011-07-29 | 2012-07-30 | 高分子電解質膜 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2017083000A Division JP6300985B2 (ja) | 2011-07-29 | 2017-04-19 | 高分子電解質膜の製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2016105410A JP2016105410A (ja) | 2016-06-09 |
JP6154035B2 true JP6154035B2 (ja) | 2017-06-28 |
Family
ID=47629789
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014521575A Active JP5899317B2 (ja) | 2011-07-29 | 2012-07-30 | 高分子電解質膜 |
JP2016006223A Active JP6154035B2 (ja) | 2011-07-29 | 2016-01-15 | 高分子電解質膜の製造方法 |
JP2017083000A Active JP6300985B2 (ja) | 2011-07-29 | 2017-04-19 | 高分子電解質膜の製造方法 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014521575A Active JP5899317B2 (ja) | 2011-07-29 | 2012-07-30 | 高分子電解質膜 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2017083000A Active JP6300985B2 (ja) | 2011-07-29 | 2017-04-19 | 高分子電解質膜の製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9761900B2 (ja) |
EP (1) | EP2737567B1 (ja) |
JP (3) | JP5899317B2 (ja) |
KR (1) | KR101767370B1 (ja) |
CN (1) | CN103718360B (ja) |
WO (1) | WO2013019047A2 (ja) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014178620A1 (ko) * | 2013-04-29 | 2014-11-06 | 주식회사 엘지화학 | 고분자 전해질막, 고분자 전해질막을 포함하는 막전극 접합체 및 막 전극 접합체를 포함하는 연료전지 |
WO2015099208A1 (ko) * | 2013-12-23 | 2015-07-02 | 한국화학연구원 | Pan 부직포 지지체에 탄화수소계 전해질을 함침시켜 제조한 복합막 및 이의 용도 |
CN104746236B (zh) * | 2013-12-25 | 2019-06-07 | 比亚迪股份有限公司 | 一种聚酰亚胺/聚氧化乙烯电缆型复合纳米纤维膜及其制备方法 |
KR101451566B1 (ko) | 2014-02-25 | 2014-10-22 | 코오롱패션머티리얼 (주) | 다공성 지지체, 이의 제조방법 및 이를 포함하는 강화막 |
KR101971269B1 (ko) * | 2014-02-25 | 2019-04-22 | 코오롱패션머티리얼 (주) | 다공성 지지체, 이의 제조방법, 및 이를 포함하는 강화막 |
KR101664205B1 (ko) * | 2014-11-26 | 2016-10-10 | 울산과학기술원 | 금속-공기 전지용 복합 분리막, 이의 제조 방법, 및 이를 포함하는 금속-공기 전지 |
CN107146903A (zh) * | 2016-05-13 | 2017-09-08 | 宁波市智能制造产业研究院 | 一种燃料电池用聚合物电解质膜 |
KR102140121B1 (ko) * | 2016-07-01 | 2020-07-31 | 주식회사 엘지화학 | 다공성 기재를 포함하는 강화-복합 전해질막 및 이의 제조방법 |
JP6942377B2 (ja) * | 2016-09-27 | 2021-09-29 | ガードネック カンパニー リミテッドGuardnec Co.,Ltd. | 多孔炭素質フィルム層を含む燃料電池用ガス拡散層 |
KR101939822B1 (ko) * | 2016-12-19 | 2019-01-18 | 경희대학교 산학협력단 | 신경전극의 제조방법 |
KR102157935B1 (ko) * | 2018-01-10 | 2020-09-18 | 주식회사 엘지화학 | 강화 분리막 제조방법, 이에 의하여 제조된 강화 분리막 및 레독스 흐름 전지 |
US11605829B2 (en) | 2018-02-28 | 2023-03-14 | Kolon Industries, Inc. | Ion exchange membrane and energy storage device comprising same |
KR102248996B1 (ko) * | 2018-02-28 | 2021-05-06 | 코오롱인더스트리 주식회사 | 이온 교환막 및 이를 포함하는 에너지 저장 장치 |
EP3874542A4 (en) * | 2018-10-31 | 2022-09-07 | Board of Regents, The University of Texas System | COMPOSITE LAYERS AND PROCESSES FOR THEIR MANUFACTURE AND USE |
CN111613821B (zh) * | 2020-06-08 | 2021-08-03 | 深圳氢时代新能源科技有限公司 | 复合聚合物电解质膜及其制备方法、燃料电池 |
WO2022071732A1 (ko) * | 2020-09-29 | 2022-04-07 | 코오롱인더스트리 주식회사 | 고분자 전해질 막의 제조 방법 및 이로 제조된 전해질 막 |
WO2023099684A1 (en) * | 2021-12-01 | 2023-06-08 | Fundació Eurecat | Fabrication method of a membrane electrode assembly (mea), mea, cell and uses thereof |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9708365D0 (en) * | 1997-04-25 | 1997-06-18 | Johnson Matthey Plc | Proton conducting membranes |
US6248469B1 (en) * | 1997-08-29 | 2001-06-19 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
JP4743356B2 (ja) * | 2000-05-15 | 2011-08-10 | 日清紡ホールディングス株式会社 | 燃料電池セパレータの製造方法、燃料電池セパレータ及び固体高分子型燃料電池 |
JP3513097B2 (ja) * | 2000-09-29 | 2004-03-31 | 株式会社東芝 | プロトン伝導性膜およびそれを用いた燃料電池 |
WO2003092656A1 (en) | 2002-05-02 | 2003-11-13 | Isotron Corporation | Chemically and/or biologically reactive compouds |
US20040146766A1 (en) * | 2003-01-14 | 2004-07-29 | Siwen Li | Proton electrolyte membranes, methods of making proton electrolyte membranes, and methods of use thereof |
US7576165B2 (en) | 2004-01-27 | 2009-08-18 | Georgia Institute Of Technology | Heterocycle grafted monomers and related polymers and hybrid inorganic-organic polymer membranes |
JP2006244920A (ja) * | 2005-03-04 | 2006-09-14 | Fujitsu Ltd | 固体電解質組成物および高分子型燃料電池 |
WO2006098318A1 (ja) * | 2005-03-15 | 2006-09-21 | Matsushita Electric Industrial Co., Ltd. | プロトン伝導体、ならびにこれを用いた電極および燃料電池 |
JP5044894B2 (ja) | 2005-04-07 | 2012-10-10 | コニカミノルタホールディングス株式会社 | 固体高分子型燃料電池用プロトン伝導性電解質膜、該プロトン伝導性電解質膜の製造方法及び固体高分子型燃料電池 |
JP5109130B2 (ja) | 2005-08-19 | 2012-12-26 | 国立大学法人 東京大学 | プロトン伝導性ハイブリッド材料及びそれを用いた燃料電池用触媒層 |
JP2008103095A (ja) * | 2006-10-17 | 2008-05-01 | Toyobo Co Ltd | 燃料電池用高分子電解質膜とその用途 |
US7709542B2 (en) | 2007-03-23 | 2010-05-04 | Agency For Science, Technology And Research | Proton-exchange composite containing nanoparticles having outer oligomeric ionomer, and methods of forming |
KR101366079B1 (ko) * | 2007-12-31 | 2014-02-20 | 삼성전자주식회사 | 고체상 프로톤 전도체 및 이를 이용한 연료전지 |
JP5347287B2 (ja) | 2008-03-14 | 2013-11-20 | Jsr株式会社 | ダイレクトメタノール型燃料電池用高分子電解質およびその用途 |
KR20100036136A (ko) * | 2008-09-29 | 2010-04-07 | 주식회사 벡셀 | 전기방사를 이용한 불화비닐계 고분자 분리막의 제조 방법 및 상기 제조 방법에 의해 제조된 리튬 2차 전지용 고분자 분리막 |
WO2010067743A1 (ja) * | 2008-12-12 | 2010-06-17 | 株式会社クラレ | 電解質積層膜、膜-電極接合体及び燃料電池 |
KR20110021217A (ko) * | 2009-08-25 | 2011-03-04 | 코오롱인더스트리 주식회사 | 연료전지용 고분자 전해질막 및 그 제조방법 |
WO2011025259A2 (ko) * | 2009-08-25 | 2011-03-03 | 주식회사 코오롱 | 연료전지용 고분자 전해질막 및 그 제조방법 |
-
2011
- 2011-07-29 KR KR1020110075531A patent/KR101767370B1/ko active IP Right Grant
-
2012
- 2012-07-30 WO PCT/KR2012/006059 patent/WO2013019047A2/en active Application Filing
- 2012-07-30 US US14/131,544 patent/US9761900B2/en active Active
- 2012-07-30 CN CN201280037622.0A patent/CN103718360B/zh active Active
- 2012-07-30 JP JP2014521575A patent/JP5899317B2/ja active Active
- 2012-07-30 EP EP12820388.2A patent/EP2737567B1/en active Active
-
2016
- 2016-01-15 JP JP2016006223A patent/JP6154035B2/ja active Active
-
2017
- 2017-04-19 JP JP2017083000A patent/JP6300985B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
KR20130013747A (ko) | 2013-02-06 |
JP6300985B2 (ja) | 2018-03-28 |
EP2737567A2 (en) | 2014-06-04 |
CN103718360B (zh) | 2016-09-14 |
WO2013019047A3 (en) | 2013-04-04 |
WO2013019047A2 (en) | 2013-02-07 |
JP5899317B2 (ja) | 2016-04-06 |
EP2737567A4 (en) | 2015-05-06 |
JP2014525127A (ja) | 2014-09-25 |
US9761900B2 (en) | 2017-09-12 |
JP2016105410A (ja) | 2016-06-09 |
KR101767370B1 (ko) | 2017-08-24 |
JP2017168446A (ja) | 2017-09-21 |
EP2737567B1 (en) | 2016-12-07 |
CN103718360A (zh) | 2014-04-09 |
US20140154594A1 (en) | 2014-06-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6300985B2 (ja) | 高分子電解質膜の製造方法 | |
US9136034B2 (en) | Polymer electrolyte membrane for a fuel cell, and method for preparing same | |
JP6235554B2 (ja) | 高分子電解質膜、その製造方法及びそれを含む膜−電極アセンブリ | |
KR101376362B1 (ko) | 연료전지용 고분자 전해질막 및 그 제조방법 | |
Gong et al. | High level of solid superacid coated poly (vinylidene fluoride) electrospun nanofiber composite polymer electrolyte membranes | |
US20150303505A1 (en) | Reinforced composite membrane for fuel cell and membrane-electrode assembly for fuel cell comprising the same | |
JP6205519B2 (ja) | 高分子電解質膜、それを含む膜−電極アセンブリ及び燃料電池 | |
JP5791732B2 (ja) | 高分子電解質及びその製造方法 | |
JP6180624B2 (ja) | 高分子電解質膜、この製造方法、及びこれを含む膜−電極アセンブリ | |
JP2020526001A (ja) | 炭素ナノ繊維紡糸層を含む燃料電池用ガス拡散層 | |
CN110197911B (zh) | 一种全钒液流电池用多孔隔膜及其制备方法和用途 | |
KR20130004615A (ko) | 연료전지용 복합 전해질막 및 그 제조방법 | |
KR20120134236A (ko) | 연료전지용 전해질막 및 그 제조방법 | |
KR20110054607A (ko) | 강화 복합 전해질 막 및 그의 제조방법 | |
KR20100098234A (ko) | 고분자 전해질 복합막 제조 방법 및 이를 이용하여 형성한 고분자 전해질 복합막을 포함하는 고분자 전해질 연료전지 | |
KR20190026543A (ko) | 고분자 전해질 연료전지용 수소이온 전도성 고분자 섬유 매트릭스 내장 전극 및 이를 포함하는 막-전극 접합체 | |
JP5867093B2 (ja) | 複合化高分子電解質膜およびその製造方法 | |
JP2011246695A (ja) | 複合化高分子電解質膜およびその製造方法 | |
JP5303838B2 (ja) | プロトン伝導性材料、それを用いて成る膜電極接合体(mea)およびその製造方法 | |
He et al. | Organic-Inorganic Hybrid Membranes for Proton Exchange Membrane Fuel Cells | |
KR20140085882A (ko) | 연료전지용 강화복합막 및 이를 포함하는 연료전지용 막-전극 어셈블리 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161011 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170105 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170131 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170419 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170509 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170531 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6154035 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |