JP2017505515A - プロトン交換膜燃料電池用の膜 - Google Patents
プロトン交換膜燃料電池用の膜 Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 153
- 239000000446 fuel Substances 0.000 title claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 162
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 238000005341 cation exchange Methods 0.000 claims abstract description 8
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001768 cations Chemical group 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 229920000412 polyarylene Polymers 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229920002530 polyetherether ketone Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002480 polybenzimidazole Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- ICMZFZGUTLNLAJ-UHFFFAOYSA-N 2,6-dimethyl-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound CC1=CC=CC2(C)OC12 ICMZFZGUTLNLAJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004962 Polyamide-imide Substances 0.000 claims description 2
- 229920002312 polyamide-imide Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 229920002313 fluoropolymer Polymers 0.000 abstract description 4
- 239000004811 fluoropolymer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 210000004027 cell Anatomy 0.000 description 25
- 229920003937 Aquivion® Polymers 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- -1 alkaline earth metal cation Chemical class 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229920000557 Nafion® Polymers 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 6
- 229920000554 ionomer Polymers 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 150000003457 sulfones Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 229920003934 Aciplex® Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920003997 Torlon® Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005362 aryl sulfone group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002863 poly(1,4-phenylene oxide) polymer Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000000075 primary alcohol group Chemical group 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UGQZLDXDWSPAOM-UHFFFAOYSA-N pyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical compound C1=C2C(=O)NC(=O)C2=CC2=C1C(=O)NC2=O UGQZLDXDWSPAOM-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is 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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- 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
-
- 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
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Conductive Materials (AREA)
Abstract
Description
- 一酸化炭素(CO)の存在は、概して触媒の被毒をもたらす。水素(燃料)が改質により得られる場合、水素は概して微量の一酸化炭素を含有する。COの存在は、それを吸着する白金ベース触媒の効率を低下させる。したがって、PEMFCの性能が低下する。一方、白金ベース触媒上のCOの吸着は、低温で有利であるが、高温では、吸着反応の負のエントロピーに起因して影響を受ける。したがって、COへの耐性は、温度と共に増加する。したがって、CO被毒に起因するPEMFCの性能低下は、高温(約140℃)で大幅に軽減され得る。
- PEMFCの熱管理は、電池がそのエネルギーの40〜50%を熱の形態で生成することを考慮すると、低温においてより複雑となる。したがって、電池が低温で動作する場合、大量のエネルギーが散逸されなければならない。逆に、電池が120〜140℃の範囲内の温度で動作する場合、電池により生成された熱は、システム温度の維持を可能にし、必要とされる冷却システムはより小さい。この点は、自動車産業における用途に特に重要である。更に、100℃を超える温度の場合、生成された熱は、他の目的(例えば熱電併給モードでの加熱)にも使用され得る。
- PFSA型膜は常に湿潤を必要とすることを考慮すると、低温において膜の加湿が不可欠である。加湿に必要な添加剤は、システムを複雑化し、その信頼性を低下させる。膜のプロトン伝導度は、ポリマーマトリックス中に含有される水の量と共に増加し、これはそもそも膜外の水の量(相対湿度)と共に増加することを考慮すると、加湿が必要である。そのような加湿は、達成及び管理するにはより一層複雑であり、温度が高い場合はなおさらエネルギーを必要とする。
- 50〜95%、有利には70〜95%のポリマーAと、
- 5〜50%、有利には5〜30%のポリマーBと
を含み、
Aがカチオン交換フッ素化ポリマーであり、
BがポリマーAとは異なる芳香族炭化水素ポリマーであり、そのポリマー鎖上に少なくとも1つの芳香環を含む、膜に関する。
を有してもよい。
R2=O、SO2、CH2、CH2-CH2、5つ又は6つの炭素原子を含む芳香環、NH、NR3(R3=1〜4つの炭素原子を含む直鎖状又は分岐状アルキル基、好ましくはメチルである)である。
- 少なくとも1種の溶媒中のポリマーA及びBの溶液を調製する工程と、
- ポリマーA及びBの溶液から膜を成形する工程と、
- 少なくとも1種の溶媒を蒸発させる工程と、
- 任意選択で、膜を酸溶液に浸漬することにより膜を再生(又は交換)する工程と、
- 膜を乾燥させる工程と
を含む。
表1は、調製された膜のそれぞれの組成を要約したものである。膜INV-1〜INV-5は、本発明による膜であり、一方膜CE-1、CE-2、及びCE-3は、先行技術による反例である。
80/20質量比のAquivion(登録商標)/S-PEEK(A/B)混合物(INV-3)の場合:
ポリマー膜A/Bの成形を、キャスト-蒸発により、ペトリ皿中における溶液の堆積後に行う。
次いで、アセンブリを、120℃で24時間熱処理し、溶媒を除去する。
室温で15分間、2リットルの超純水中に浸漬し、膜が分離するまで膜表面を覆うことにより、膜をその支持体から分離する。そのような浸漬は、このようにして可能な溶媒残渣の除去を可能にする。
自立式の膜を、1.5Lの塩酸(HCl、1M、室温)に24時間浸漬し、特に、おそらくはカチオンの形態である、又は互いに反応した可能性のあるスルホン芳香族炭化水素ポリマー(B)上の-SO3X基の交換を行う。
次いで、真空下、50℃で2日間、次いで80℃で2日間膜を乾燥させる。乾燥の最後にのみ、膜を特性決定する。
2-1/動的機械熱分析(DMTA)
DMTA Q800デバイス(TA Instruments社)を用いて、膜INV-2、INV-3及びINV-4の動的機械熱分析を行った。
ATG Q50デバイス(TA Instruments社)を用いて、Aquivion(登録商標)/S-PEEK膜(INV-1、INV-3、及びINV-5)のサーモグラムを記録した。
質量m0の初期乾燥試料から、超純水中の15℃及び80℃での異なる浸漬時間後に行われる計量(mt)により、材料の吸収率を決定する。
膨潤率(wt.%)=[(mt-m0)/m0]×100
各試料を、1Lの超純水中に、室温で24時間浸漬する。
膜を5×5cm2のサイズに切断し、次いで燃料電池試験単一セルに組み込む。
Claims (11)
- プロトン交換膜燃料電池用の膜であって、膜の総質量に対する質量で、
- 50〜95%のポリマーAと、
- 5〜50質量%のポリマーBと
の混合物を含み、
Aが、-SO3 -X+基、-PO3 -X+基、及び-COO-X+基(式中、Xは、水素原子又はカチオンである)を含む群から選択される基を含むフッ素化カチオン交換ポリマーであり、
Bが、ポリマーAとは異なる芳香族炭化水素ポリマーであり、そのポリマー鎖上に少なくとも1つの芳香環を含み、Bが、スルホン酸基-SO3Hで官能化されている、膜。 - ポリマーAが、10,000〜10,000,000g/molの範囲内の分子量を有すること、及びポリマーBが、1,000〜200,000g/molの範囲内の分子量を有することを特徴とする、請求項1に記載のプロトン交換膜燃料電池用の膜。
- ポリマーAが、式
のスルホン酸ペルフルオロ化ポリマーであることを特徴とする、請求項1又は2に記載のプロトン交換膜燃料電池用の膜。 - ポリマーBが、ポリアリーレン、エーテルポリアリーレン、フッ素化エーテルポリアリーレン、ポリスルホン、ポリベンゾイミダゾール、ポリ(エーテルケトン)、ポリ(エーテルケトンケトン)、ポリ(エーテルエーテルケトン)、ポリ(エーテルスルホン)、ポリ(エーテルイミド)、ポリカーボネート、ポリ-2,6-ジメチルフェニレンオキシド、ポリアミド-イミド、ポリピロメリットイミドを含む群から選択されることを特徴とする、請求項1から3のいずれか一項に記載のプロトン交換膜燃料電池用の膜。
- 70〜95質量%のポリマーA及び5〜30質量%のポリマーBを含むことを特徴とする、請求項1から4のいずれか一項に記載のプロトン交換膜燃料電池用の膜。
- 請求項1から5のいずれか一項に記載の膜を調製する方法であって、
- 少なくとも1種の溶媒中のポリマーA及びBの溶液を調製する工程と、
- ポリマーA及びBの溶液から膜を成形する工程と、
- 少なくとも1種の溶媒を蒸発させる工程と、
- 膜を乾燥させる工程と
を含む方法。 - 前記溶媒が、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシド、及び水/アルコール混合物を含む群から選択されることを特徴とする、請求項6に記載の方法。
- 前記膜の成形が、キャスト-蒸発、コーティング、スパッタ堆積、フレキソ印刷堆積、スピンコーティング、及びシルクスクリーン堆積を含む群から選択される技術に従って行われることを特徴とする、請求項6又は7に記載の方法。
- 前記乾燥工程の前に、膜が酸溶液に浸漬され、次いで水中で洗浄されることを特徴とする、請求項6から8のいずれか一項に記載の方法。
- 前記酸溶液が2未満のpHを有すること、及び浸漬時間が15分〜48時間の範囲内であることを特徴とする、請求項9に記載の方法。
- 前記酸溶液が、0.5〜12mol/Lの範囲内の濃度を有する塩酸溶液であることを特徴とする、請求項9又は10に記載の方法。
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