JP2006190627A - Solid polyelectrolyte membrane having reinforcement material - Google Patents
Solid polyelectrolyte membrane having reinforcement material Download PDFInfo
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- JP2006190627A JP2006190627A JP2005003036A JP2005003036A JP2006190627A JP 2006190627 A JP2006190627 A JP 2006190627A JP 2005003036 A JP2005003036 A JP 2005003036A JP 2005003036 A JP2005003036 A JP 2005003036A JP 2006190627 A JP2006190627 A JP 2006190627A
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- 239000012528 membrane Substances 0.000 title claims abstract description 112
- 239000007787 solid Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title abstract description 8
- 230000002787 reinforcement Effects 0.000 title abstract 2
- 229920000867 polyelectrolyte Polymers 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 128
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 81
- 239000000446 fuel Substances 0.000 claims abstract description 48
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 18
- 239000005518 polymer electrolyte Substances 0.000 claims description 38
- 229920000728 polyester Polymers 0.000 claims description 25
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 16
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 210000004027 cell Anatomy 0.000 description 47
- 239000012779 reinforcing material Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 22
- 230000008859 change Effects 0.000 description 21
- 238000005470 impregnation Methods 0.000 description 16
- 229920002480 polybenzimidazole Polymers 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000004693 Polybenzimidazole Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000010408 film Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 8
- 210000000170 cell membrane Anatomy 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003880 polar aprotic solvent Substances 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002577 polybenzoxazole Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- DPZVOQSREQBFML-UHFFFAOYSA-N 3h-pyrrolo[3,4-c]pyridine Chemical compound C1=NC=C2CN=CC2=C1 DPZVOQSREQBFML-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- 229920000544 Gore-Tex Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Conductive Materials (AREA)
Abstract
Description
本発明は、燃料電池用電解質膜として有用な高分子固体電解質膜に関する。 The present invention relates to a polymer solid electrolyte membrane useful as an electrolyte membrane for fuel cells.
近年、電解質として高分子固体電解質膜を用いた燃料電池が、小型軽量化が可能であり、かつ比較的低温でも高い出力密度が得られることから注目され、特に自動車用途に向けた開発が加速されている。
このような目的に用いられる高分子固体電解質膜材料には、優れたプロトン伝導度、適度な保水性、また水素ガス、酸素ガス等に対するガスバリア性などが要求される。このような要件を満たす材料として、スルホン酸基やホスホン酸基を主鎖、あるいは側鎖の末端に有する高分子が種々検討され、例えばスルホン化ポリスチレンなど多くの材料が提案されてきている。
In recent years, fuel cells using solid polymer electrolyte membranes as electrolytes have attracted attention because they can be reduced in size and weight, and high power density can be obtained even at relatively low temperatures, and development for automotive applications in particular has been accelerated. ing.
The polymer solid electrolyte membrane material used for such purposes is required to have excellent proton conductivity, appropriate water retention, gas barrier properties against hydrogen gas, oxygen gas, and the like. As materials satisfying such requirements, various polymers having a sulfonic acid group or a phosphonic acid group at the main chain or side chain end have been studied, and many materials such as sulfonated polystyrene have been proposed.
しかし、実際の燃料電池運転条件下では、電極において高い酸化力を有する活性酸素種が発生し、特に長期に渡り燃料電池を安定に運転させるためには、このような過酷な酸化雰囲気下での耐久性が要求される。現在までに提案されている多くの炭化水素系材料は、燃料電池の運転の初期特性に関しては優れた特性を示すものが多いが、長期運転に関しては充分な耐性が示せない。
現在、実用化に向けた検討では、下記一般式（１）で表されるパーフルオロカーボンスルホン酸ポリマーが主に用いられている。
However, under actual fuel cell operating conditions, active oxygen species with high oxidizing power are generated at the electrode, and in order to operate the fuel cell stably over a long period of time, it is necessary to operate under such a harsh oxidizing atmosphere. Durability is required. Many of the hydrocarbon-based materials that have been proposed so far often exhibit excellent characteristics with respect to the initial characteristics of the fuel cell operation, but do not exhibit sufficient resistance for long-term operation.
Currently, perfluorocarbon sulfonic acid polymers represented by the following general formula (1) are mainly used in studies for practical use.
これらのパーフルオロカーボンスルホン酸ポリマー膜は、骨格が全フッ素化されているために化学的に極めて高い耐久性を示し、先述の炭化水素系膜に比べ、より過酷な運転条件でも使用することが可能である。しかし、これらのパーフルオロカーボンスルホン酸ポリマーは、ガラス転移点が約１２０℃で、実使用温度域に近いことが良く知られ、この結果、室温程度での運転では充分な物理強度をもつが、８０℃以上の温度領域では物理強度が不十分である。
従って、パーフルオロカーボンスルホン酸ポリマー膜として良く用いられるものに、Ｎａｆｉｏｎ（デュポン社製 登録商標）やＦｌｅｍｉｏｎ（旭硝子社製 登録商標）などがあるが、これらの膜は例えばホットプレス法により電解質膜と電極を接合する際に膜が破損しガスのリークを生じたり、電極内の短絡が生じやすいという問題があった。また実際の運転時においても充分な加湿環境の下で長期における耐久性を発揮することができなかった。この耐久性については、高分子固体電解質膜の乾燥時に対する含水時の寸法の変化が大きく局所的な歪が高分子膜の劣化や破壊の基点となるからである。
These perfluorocarbon sulfonic acid polymer membranes exhibit extremely high chemical durability due to the fully fluorinated skeleton, and can be used even in harsh operating conditions compared to the hydrocarbon membranes described above. It is. However, it is well known that these perfluorocarbon sulfonic acid polymers have a glass transition point of about 120 ° C. and are close to the actual use temperature range. As a result, the perfluorocarbon sulfonic acid polymer has sufficient physical strength when operated at about room temperature. The physical strength is insufficient in the temperature range of ℃ or higher.
Accordingly, Nafion (registered trademark manufactured by DuPont) and Flemion (registered trademark manufactured by Asahi Glass Co., Ltd.) and the like are often used as perfluorocarbon sulfonic acid polymer membranes. When joining the films, there was a problem that the film was broken to cause gas leakage or a short circuit in the electrode. Further, even during actual operation, long-term durability could not be exhibited in a sufficiently humidified environment. This durability is because the dimensional change at the time of moisture content with respect to the time of drying of the polymer solid electrolyte membrane is large, and local strain becomes a base point of deterioration or breakage of the polymer membrane.
これに対して、補強材を用いることが検討されている。補強材としては一般にＰＴＦＥやＰＦＡ（テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体）、ＰＶＤＦ（ポリビニリデンフルオライド）、ＦＥＰ（テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体）等のフッ素系高分子またはＰＥ（ポリエチレン）やＰＰ（ポリプロピレン）等の熱可塑性樹脂、またＰＩ（ポリイミド）、ＰＳＦ（ポリスルホン）、ＰＥＳ（ポリエーテルスルホン）、ＰＥＥＫ（ポリエーテルエーテルケトン）、ＰＰＳＳ（ポリフェニレンスルフィドスルフォン）、ＰＰＯ（ポリフェニレンオキシド）、ＰＥＫ（ポリエーテルケトン）、ＰＢＩ（ポリベンズイミダゾール）、ＰＰＳ（ポリフェニレンスルフィド）、ＰＰＰ（ポリパラフェニレン）、ＰＰＱ（ポリフェニルキノキサリン）、ポリベンゾオキサゾール（ＰＢＯ）、ポリベンゾチアゾール（ＰＢＴ）、ポリパラフェニレンテレフタルアミド（ＰＰＴＡ）等のエンジニアリングプラスチックからなる均質な多孔質膜を挙げることができるが、その孔径がおよそ０．０１〜１μｍと小さい場合にはパーフルオロカーボンスルホン酸ポリマーの充填が十分には行なえず空孔が残るという問題があった。また孔径がおよそ１〜１０μｍというより大きなものも存在するが、この場合には空孔率を本発明のように４０％以上とした場合には補強材の強度が十分ではなく、特に６０μｍ以下の薄膜としては実用には供さなかった（特許文献１，３，４，９，１０，１１，１２，１３）。即ち、均一の多孔質膜では、充分な耐久性を確保することができていないのである。 On the other hand, use of a reinforcing material has been studied. As the reinforcing material, generally, a fluorine-based polymer such as PTFE, PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PVDF (polyvinylidene fluoride), FEP (tetrafluoroethylene-hexafluoropropylene copolymer), or the like Thermoplastic resins such as PE (polyethylene) and PP (polypropylene), PI (polyimide), PSF (polysulfone), PES (polyethersulfone), PEEK (polyetheretherketone), PPSS (polyphenylene sulfide sulfone), PPO ( Polyphenylene oxide), PEK (polyetherketone), PBI (polybenzimidazole), PPS (polyphenylene sulfide), PPP (polyparaphenylene), PPQ (polyphenylquinoxaline) A homogeneous porous film made of engineering plastics such as polybenzoxazole (PBO), polybenzothiazole (PBT), polyparaphenylene terephthalamide (PPTA) can be mentioned, and the pore diameter is about 0.01 to 1 μm. If it is small, there is a problem that the perfluorocarbon sulfonic acid polymer cannot be sufficiently filled and vacancies remain. There are also larger pore diameters of about 1 to 10 μm, but in this case, when the porosity is 40% or more as in the present invention, the strength of the reinforcing material is not sufficient, especially 60 μm or less. As a thin film, it was not put into practical use (Patent Documents 1, 3, 4, 9, 10, 11, 12, 13). That is, sufficient durability cannot be ensured with a uniform porous membrane.
加えて均一の多孔質膜の補強材にパーフルオロカーボンスルホン酸ポリマーを含浸させたものは複合固体高分子電解質膜としての強度を十分に発揮させるためには少なくとも１４０℃以上の加熱が必要であるため、補強材の材質によってはこのような加熱をするともともとあった補強材の穴が閉塞してしまい電解質膜として使用するには至らなかった（特許文献２）。
一方、均質な多孔質膜ではなく各種の繊維からなる不織布、織布、または紙様のシートを補強材とする電解質膜も検討されている。
例えばアラミド繊維やポリフェニレンサルファイド繊維よりなる不織布が用いられているが、本発明と同様の複合高分子固体電解質膜とした場合には十分な耐久性が得られない（特許文献５，６，８，１４）。これは恐らくアラミドやポリフェニレンスルフィドが耐加水分解性に劣り、吸水性が高いために、これを補強材として用いた場合には複合固体高分子電解質膜としての化学的な耐久性が劣るのではないかと推測される。そのためアラミド繊維の表面をフッ素コーティングする等の方法が検討されているが充分な耐久性を得るにはいたっていない。
In addition, a material in which a uniform porous membrane reinforcing material is impregnated with a perfluorocarbon sulfonic acid polymer needs to be heated to at least 140 ° C. in order to sufficiently exert the strength as a composite solid polymer electrolyte membrane. Depending on the material of the reinforcing material, when such heating is performed, the hole of the originally reinforcing material is blocked and cannot be used as an electrolyte membrane (Patent Document 2).
On the other hand, an electrolyte membrane using a nonwoven fabric, a woven fabric, or a paper-like sheet made of various fibers instead of a homogeneous porous membrane as a reinforcing material has been studied.
For example, a nonwoven fabric made of aramid fiber or polyphenylene sulfide fiber is used, but sufficient durability cannot be obtained when the composite polymer solid electrolyte membrane is the same as the present invention (Patent Documents 5, 6, 8, 14). This is probably because aramid and polyphenylene sulfide are inferior in hydrolysis resistance and have high water absorption, so when used as a reinforcing material, chemical durability as a composite solid polymer electrolyte membrane is not inferior. I guess that. For this reason, methods such as fluorine coating on the surface of aramid fibers have been studied, but sufficient durability has not been achieved.
特許文献７にはフィブリル状、織布状、不織布状のパーフルオロカーボン重合体で補強された陽イオン交換膜が提案されているが含水時の寸法変化を抑える効果が十分ではなかった。
このように特に９０℃以上の温度での長時間運転を行ってもクロスリークが発生せず、なおかつ固体高分子型燃料電池の実用化の観点から機械特性が優れ、また乾燥時に対する含水時の寸法変化が少ないという耐久性を有するものはなかった。
In this way, even if the operation is performed at a temperature of 90 ° C. or more for a long time, cross leak does not occur, the mechanical properties are excellent from the viewpoint of practical use of the polymer electrolyte fuel cell, and when the water content is higher than the dry time. None had the durability that the dimensional change was small.
即ち、本発明は７０〜８０℃という温度はいうまでもなく、さらには９０℃以上の温度での長時間運転を行ってもクロスリークが発生せず、なおかつ固体高分子型燃料電池の実用化の観点から機械特性が優れ、また乾燥時に対する含水時の寸法の変化が少ないという耐久性の高い燃料電池用の高分子固体電解質膜を提供するものである。 That is, in the present invention, it goes without saying that the temperature is 70 to 80 ° C. Furthermore, even if the operation is performed for a long time at a temperature of 90 ° C. or more, cross leak does not occur, and the solid polymer fuel cell is put to practical use. In view of the above, the present invention provides a solid polymer electrolyte membrane for a fuel cell that is excellent in mechanical properties and has a high durability with little change in dimensions when wet with respect to dryness.
本発明者は上記課題を解決すべく鋭意検討した結果、芳香族液晶ポリエステル不織布を補強材に有する複合固体高分子電解質膜とすることで乾燥時に対する含水時の寸法の変化が極めて小さく、７０〜８０℃さらには９０℃以上の温度での長時間の運転を行ってもクロスリークが発生せずまた機械特性が優れた耐久性の高い燃料電池用の高分子固体電解質膜を作りうることを見いだし本発明に至った。
すなわち本発明は
１、 芳香族液晶ポリエステルからなる不織布を有することを特徴とする高分子固体電解質膜。
２、 該不織布の空隙率が４０〜９５％であって、かつ、空隙が該高分子固体電解質で充填されていることを特徴とする１に記載の高分子固体電解質膜。
３、 該高分子固体電解質が下記式（1）で示されるパーフルオロカーボンスルホン酸ポリマーからなるイオン交換樹脂であることを特徴とする１又は２に記載の高分子固体電解質膜。
［CF２CF２］a−［CF２−CF(−O−CF２−CF(CF３））ｂ−O−（CF２）ｆ−SO３H）］ｇ（１）
（式中、０≦ａ＜１、０＜ｇ≦１，ａ＋ｇ＝１，０≦ｂ≦３、１≦ｆ≦８である。）
４、 該高分子固体電解質が下記式（２）で示されるパーフルオロカーボンスルホン酸ポリマーからなるイオン交換樹脂であることを特徴とする１又は２に記載の高分子固体電解質膜。
［CF２CF２］a−［CF２−CF(−O−CF２−CF(CF３））ｂ−O−（CF２）ｆ−SO３H）］ｇ（２）
（式中、０≦ａ＜１、０＜ｇ≦１，ａ＋ｇ＝１，０≦ｂ＜１、１≦ｆ≦８である。）
５、 該高分子固体電解質膜が、少なくとも高分子固体電解質（ａ）と、塩基性重合体（ｂ）とを含有し、該（ａ）と該（ｂ）の間に、該（ａ）の含有率（（ａ）／（（ａ）＋（ｂ））×１００）が５０．００〜９９．９９９質量％、該（ｂ）の含有率（（ｂ）／（（ａ）＋（ｂ））×１００）が０．００１〜５０．００質量％なる関係を有することを特徴とする１〜４の何れかに記載の高分子固体電解質膜。
６、 １〜５のいずれかに記載の高分子固体電解質膜を介してアノードとカソードが対向してなる膜／電極接合体。
７、 ６に記載の膜／電極接合体を包含してなることを特徴とする高分子固体電解質型燃料電池。
As a result of intensive studies to solve the above-mentioned problems, the present inventor made a composite solid polymer electrolyte membrane having an aromatic liquid crystal polyester nonwoven fabric as a reinforcing material, so that the change in dimensions when wet with respect to dryness was extremely small. It has been found that cross-leakage does not occur even when operated for a long time at a temperature of 80 ° C. or even 90 ° C. or higher, and that a solid polymer electrolyte membrane for fuel cells with excellent mechanical properties can be made. The present invention has been reached.
That is, the present invention is 1. A polymer solid electrolyte membrane comprising a nonwoven fabric made of an aromatic liquid crystalline polyester.
2. The polymer solid electrolyte membrane according to 1, wherein the non-woven fabric has a porosity of 40 to 95%, and the voids are filled with the polymer solid electrolyte.
3. The polymer solid electrolyte membrane according to 1 or 2, wherein the polymer solid electrolyte is an ion exchange resin made of a perfluorocarbon sulfonic acid polymer represented by the following formula (1).
[CF 2 CF 2] a - [CF 2 -CF (-O-CF 2 -CF (CF 3)) b -O- (CF 2) f -SO 3 H)] g (1)
(Where 0 ≦ a <1, 0 <g ≦ 1, a + g = 1, 0 ≦ b ≦ 3, 1 ≦ f ≦ 8)
4. The polymer solid electrolyte membrane according to 1 or 2, wherein the polymer solid electrolyte is an ion exchange resin made of a perfluorocarbon sulfonic acid polymer represented by the following formula (2).
[CF 2 CF 2] a - [CF 2 -CF (-O-CF 2 -CF (CF 3)) b -O- (CF 2) f -SO 3 H)] g (2)
(Where 0 ≦ a <1, 0 <g ≦ 1, a + g = 1, 0 ≦ b <1, 1 ≦ f ≦ 8)
5. The polymer solid electrolyte membrane contains at least a polymer solid electrolyte (a) and a basic polymer (b), and between (a) and (b), Content ((a) / ((a) + (b)) × 100) is 50.00 to 99.999 mass%, content of (b) ((b) / ((a) + (b) ) × 100) has a relationship of 0.001 to 50.00% by mass. 5. The polymer solid electrolyte membrane according to any one of 1 to 4, wherein
6. A membrane / electrode assembly in which an anode and a cathode face each other through the polymer solid electrolyte membrane according to any one of 1 to 5.
7. A solid polymer electrolyte fuel cell comprising the membrane / electrode assembly according to 7 or 6.
本発明の高分子固体電解質膜は、機械特性が優れ、また乾燥時に対する含水時の寸法の変化が少なく、燃料電池の高分子固体電解質膜に用いた場合の９０℃以上での長時間運転を行ってもクロスリークが発生しないため、耐久性の高い燃料電池用の高分子固体電解質膜となりうる。 The polymer solid electrolyte membrane of the present invention is excellent in mechanical properties, has little change in dimensions when wet with respect to dryness, and can be operated for a long time at 90 ° C. or higher when used in a polymer solid electrolyte membrane of a fuel cell. Since no cross-leak occurs even if it is performed, it can be a highly durable polymer solid electrolyte membrane for fuel cells.
以下に本発明を詳細に説明する。
本発明の高分子固体電解質膜に芳香族液晶ポリエステルの不織布は補強材として作用する。具体的には下記一般式（３）に示す構造単位からなる重合体であり、サーモトロピック液晶ポリエステルに分類される。
The present invention is described in detail below.
The nonwoven fabric of aromatic liquid crystal polyester functions as a reinforcing material in the polymer solid electrolyte membrane of the present invention. Specifically, it is a polymer composed of a structural unit represented by the following general formula (3), and is classified as a thermotropic liquid crystal polyester.
一般式（３）に示す構造単位のみからなる重合体が最も好ましいが、本発明の趣旨に反さない範囲で（４）に例示されるような構造単位を含む形の共重合体としても何ら問題がない。
A polymer consisting only of the structural unit represented by the general formula (3) is most preferable, but any copolymer having a structural unit as exemplified in (4) may be used without departing from the spirit of the present invention. there is no problem.
芳香族液晶ポリエステルは吸水率が特に少なく、かつ機械的強度並びに寸法精度が優れており、これを不織布にしたものを補強材として有する複合高分子固体電解質膜は固体高分子型燃料電池に用いた場合には極めて良好な耐久性および性能を有する。
芳香族液晶ポリエステルは当業者に知られている通常の方法により溶融紡糸することにより繊維が得られる。芳香族液晶ポリエステルより得られる繊維は高度に配向しているため、紡糸しただけで十分高い強度を有しているが、紡糸繊維を高温で一定時間熱処理を行うことにより更に強度が増大するので、熱処理したあとの繊維を用いることも好ましい。
得られた芳香族液晶ポリエステル繊維は常法により不織布にすることにより本発明の燃料電池用複合高分子固体電解質膜の補強材として用いることができる。
Aromatic liquid crystalline polyester has a particularly low water absorption and excellent mechanical strength and dimensional accuracy. A composite polymer solid electrolyte membrane having a non-woven fabric as a reinforcing material was used for a polymer electrolyte fuel cell. In some cases it has very good durability and performance.
Aromatic liquid crystalline polyester can be obtained by melt spinning by a conventional method known to those skilled in the art. Since the fiber obtained from the aromatic liquid crystal polyester is highly oriented, it has a sufficiently high strength just by spinning, but the strength is further increased by heat treating the spun fiber at a high temperature for a certain time, It is also preferable to use the fiber after heat treatment.
The obtained aromatic liquid crystal polyester fiber can be used as a reinforcing material for the composite polymer solid electrolyte membrane for fuel cells of the present invention by forming a nonwoven fabric by a conventional method.
本発明の燃料電池用固体高分子電解質膜の補強材としては芳香族液晶ポリエステル繊維から得られる不織布を用いるが、本発明の趣旨に反しない範囲でＰＥＴ繊維、ガラス繊維等を混合しても良いが、本来の目的である燃料電池用固体高分子電解質膜の補強材としての耐久性を十分に発揮するためには９０％以上が芳香族液晶ポリエステルからなることが望ましい。また芳香族液晶ポリエステルは本発明の趣旨に反しない範囲で若干の脂肪族構造を主鎖、または側鎖に含んでも良いが本来の目的である燃料電池用固体高分子電解質膜の補強材としての耐久性を十分に発揮するためには９０％以上が芳香族液晶ポリエステルからなることが望ましい。
本発明の高分子固体電解質膜は補強材として上記の芳香族液晶ポリエステルの不織布を含有した複合体を形成しており、補強材が高分子固体電解質膜中に包埋されていることが好ましい。
As a reinforcing material for the solid polymer electrolyte membrane for a fuel cell of the present invention, a nonwoven fabric obtained from aromatic liquid crystal polyester fiber is used, but PET fiber, glass fiber, etc. may be mixed within the range not departing from the gist of the present invention. However, 90% or more of the liquid crystal polyester is desirably composed of aromatic liquid crystalline polyester in order to fully exhibit the durability as a reinforcing material for the solid polymer electrolyte membrane for fuel cells, which is the original purpose. In addition, the aromatic liquid crystalline polyester may contain some aliphatic structure in the main chain or side chain as long as it does not contradict the gist of the present invention, but as a reinforcing material for the solid polymer electrolyte membrane for fuel cells, which is the original purpose. In order to sufficiently exhibit durability, it is desirable that 90% or more is made of an aromatic liquid crystal polyester.
The polymer solid electrolyte membrane of the present invention forms a composite containing the above-mentioned aromatic liquid crystal polyester nonwoven fabric as a reinforcing material, and the reinforcing material is preferably embedded in the polymer solid electrolyte membrane.
補強材として用いる芳香族液晶ポリエステル不織布の厚みは、５μｍ以上、６０μｍ以下であり、より好ましくは１０μｍ以上、５０μｍ以下である。厚みが５μｍよりも薄いと高分子固体電解質を含浸等する工程中で破損等の不良が生じ、また含浸後の高分子固体電解質膜の機械特性が十分ではない。一方、厚みが６０μｍよりも厚いと、電気抵抗が大きくなり燃料電池としての特性は悪くなる。
また本発明で用いることができる補強材としての不織布の空孔率は４０〜９５％が好ましく、より好ましくは５０〜９０％である。４０％よりも空孔率が低いと固体電解質膜としてのプロトン伝導性が低下し、一方で９５％よりも空孔率が高くなると不織布の本来の強度が保てなくなるので好ましくない。
本発明の高分子固体電解質膜に補強材として用いられる芳香族液晶ポリエステル不織布は表面処理を行うこともできる。この処理を行うとその後の高分子固体電解質の含浸を好適に行うことができる。このような表面処理の一例としては、コロナ放電処理、紫外線照射処理、プラズマ処理が挙げることができる。
The thickness of the aromatic liquid crystal polyester nonwoven fabric used as the reinforcing material is 5 μm or more and 60 μm or less, more preferably 10 μm or more and 50 μm or less. If the thickness is less than 5 μm, defects such as breakage occur in the process of impregnating the polymer solid electrolyte, and the mechanical properties of the polymer solid electrolyte membrane after impregnation are not sufficient. On the other hand, if the thickness is greater than 60 μm, the electrical resistance increases and the characteristics as a fuel cell deteriorate.
The porosity of the nonwoven fabric as a reinforcing material that can be used in the present invention is preferably 40 to 95%, more preferably 50 to 90%. If the porosity is lower than 40%, the proton conductivity as the solid electrolyte membrane is lowered. On the other hand, if the porosity is higher than 95%, the original strength of the nonwoven fabric cannot be maintained, which is not preferable.
The aromatic liquid crystal polyester nonwoven fabric used as a reinforcing material for the polymer solid electrolyte membrane of the present invention can be subjected to surface treatment. When this treatment is performed, the subsequent impregnation of the polymer solid electrolyte can be suitably performed. Examples of such surface treatments include corona discharge treatment, ultraviolet irradiation treatment, and plasma treatment.
次に、本発明の高分子固体電解質膜の電解質成分である高分子固体電解質について説明する。
本発明で用いられる高分子固体電解質は、イオン交換性を有する樹脂であれば構わないが、フッ素系イオン交換樹脂であることが好ましく、中でもパーフルオロカーボンスルホン酸ポリマーであることがより好ましい。
パーフルオロカーボンスルホン酸ポリマーは具体的には、下記一般式（１）で表される。
Next, the polymer solid electrolyte that is the electrolyte component of the polymer solid electrolyte membrane of the present invention will be described.
The solid polymer electrolyte used in the present invention may be any resin having ion exchange properties, but is preferably a fluorine ion exchange resin, and more preferably a perfluorocarbon sulfonic acid polymer.
The perfluorocarbon sulfonic acid polymer is specifically represented by the following general formula (1).
一般式（１）中、ｂの範囲が代わると高分子固体電解質膜のガラス転移点が変わる。１≦ｂ≦３の範囲でガラス転移点がおよそ１２０℃以下であるが、ｂが１以下、０に近づくにつれてガラス転移点がおよそ１４０℃を超える。従って、ｂはより好ましくは０≦ｂ＜１である。
このポリマーは、通常、パーフルオロビニルエーテルモノマーとテトラフルオロエチレン（ＴＦＥ）を共重合して得られる熱可塑性の下記一般式（５）で表されるパーフルオロカーボンスルホニルフルオライドポリマーを加水分解反応を施すことによって得られる。
In the general formula (1), when the range of b is changed, the glass transition point of the polymer solid electrolyte membrane is changed. In the range of 1 ≦ b ≦ 3, the glass transition point is approximately 120 ° C. or less, but as b approaches 1 or less and 0, the glass transition point exceeds approximately 140 ° C. Therefore, b is more preferably 0 ≦ b <1.
This polymer is usually obtained by subjecting a thermoplastic perfluorocarbonsulfonyl fluoride polymer represented by the following general formula (5) obtained by copolymerizing a perfluorovinyl ether monomer and tetrafluoroethylene (TFE) to a hydrolysis reaction. Obtained by.
次に高分子固体電解質膜に含まれる添加剤としての塩基性重合体について説明する。
本発明の高分子固体電解質膜では、特に塩基性重合体を高分子固体電解質成分に添加剤として含有させることによって耐久性が飛躍的に向上する。塩基性重合体としては窒素含有脂肪族塩基性重合体や窒素含有芳香族塩基性重合体が挙げられる。
窒素含有脂肪族塩基性重合体の例としては、ポリエチレンイミンが挙げられる。窒素含有芳香族塩基性重合体の例としては、ポリアニリン、及び複素環式化合物であるポリベンズイミダゾール、ポリピリジン、ポリピリミジン、ポリビニルピリジン、ポリイミダゾール、ポリピロリジン、ポリビニルイミダゾール等が挙げられる。この中でもポリベンズイミダゾールは耐熱性が高いことから特に好ましい。
ポリベンズイミダゾールとしては、一般式（６）、一般式（７）に表される化合物、一般式（８）で表されるポリ２，５−ベンズイミダゾール等が挙げられる。
Next, the basic polymer as an additive contained in the polymer solid electrolyte membrane will be described.
In the solid polymer electrolyte membrane of the present invention, durability is dramatically improved by incorporating a basic polymer as an additive in the solid polymer electrolyte component. Examples of the basic polymer include a nitrogen-containing aliphatic basic polymer and a nitrogen-containing aromatic basic polymer.
Examples of nitrogen-containing aliphatic basic polymers include polyethyleneimine. Examples of the nitrogen-containing aromatic basic polymer include polyaniline and heterocyclic compounds such as polybenzimidazole, polypyridine, polypyrimidine, polyvinylpyridine, polyimidazole, polypyrrolidine, and polyvinylimidazole. Among these, polybenzimidazole is particularly preferable because of its high heat resistance.
Examples of the polybenzimidazole include compounds represented by general formula (6) and general formula (7), and poly 2,5-benzimidazole represented by general formula (8).
ある。Ｒは一般式（６）で定義したものと同じである。
以上のようなポリベンズイミダゾールの中でも、下記化学式（９）で表されるポリ[２、２’−（ｍ−フェニレン）−５，５’−ビベンゾイミダゾール]が特に好ましい。
Among the polybenzimidazoles as described above, poly [2,2 ′-(m-phenylene) -5,5′-bibenzimidazole] represented by the following chemical formula (9) is particularly preferable.
塩基性重合体（ｂ）の含有率は、上記のように成分（ａ）と成分（ｂ）の合計質量に対して０．００１〜５０．０００質量％であり、好ましくは０．００５〜２０．０００質量％、より好ましくは０．０１０〜１０．０００質量％、さらに好ましくは０．１００〜５．０００質量％、最も好ましくは０．１００〜２．０００質量％である。塩基性重合体（ｂ）の含有率を上記の範囲（０．００１〜５０．０００質量％）に設定することにより、良好なプロトン伝導度を維持したまま、高耐久性を有する高分子固体電解質膜を得ることができる。
The content rate of a basic polymer (b) is 0.001-50000 mass% with respect to the total mass of a component (a) and a component (b) as mentioned above, Preferably it is 0.005-20. 0.000% by mass, more preferably 0.010 to 10.000% by mass, still more preferably 0.100 to 5.000% by mass, and most preferably 0.100 to 2.000% by mass. By setting the content of the basic polymer (b) in the above range (0.001 to 50.000 mass%), a polymer solid electrolyte having high durability while maintaining good proton conductivity A membrane can be obtained.
本発明の高分子固体電解質膜の厚みは制限されないが、１０〜１５０μｍであることが好ましく、より好ましくは１５〜１００μｍ、最も好ましくは２０〜７５μｍである。膜厚が厚いほど耐久性は良くなる一方で、初期特性は悪くなるため、上記の範囲（１０〜１５０μｍ）で膜厚を設定するのが好ましい。
本発明の高分子固体電解質膜の製造法は特に限定されないが、上記の高分子固体電解質が水、アルコール類等のプロトン溶媒や、ＤＭＦ（ジメチルホルムアミド）、ＤＭＡｃ（ジメチルアセトアミド）、ＤＭＳＯ（ジメチルスルホキサイド）、ＮＭＰ（Ｎ−メチル−２−ピロリドン）等の極性非プロトン溶媒、或いは、その混合溶媒に溶解あるいは分散した混合液（含浸液と呼ぶ）に補強材を浸漬、含浸し次いで乾燥する方法が挙げられる。また、補強材の上に上記の高分子固体電解質が溶解あるいは分散した液を塗布して含浸、乾燥する方法も挙げられる。この方法以外にもスプレーや刷毛塗り等でも含浸できるがいずれの方法でも構わない。また含浸後に不織布の表面に付着した余分な高分子固体電解質はスクレーパ、ワイパー、エアナイフ、ローラ等で掻き落として付着量を限定することが好ましい。このような方法で作成した含浸後の高分子固体電解質膜に対して別途用意した高分子固体電解質膜を加熱下でプレスしてさらに複合することもできる。
The thickness of the polymer solid electrolyte membrane of the present invention is not limited, but is preferably 10 to 150 μm, more preferably 15 to 100 μm, and most preferably 20 to 75 μm. The thicker the film thickness, the better the durability, but the initial characteristics deteriorate. Therefore, it is preferable to set the film thickness within the above range (10 to 150 μm).
The production method of the polymer solid electrolyte membrane of the present invention is not particularly limited, but the polymer solid electrolyte may be a proton solvent such as water or alcohols, DMF (dimethylformamide), DMAc (dimethylacetamide), DMSO (dimethylsulfone). Kiss), NMP (N-methyl-2-pyrrolidone) or other polar aprotic solvent, or a mixed solution dissolved or dispersed in the mixed solvent (referred to as impregnating solution), impregnated with the reinforcing material, and then dried. A method is mentioned. Moreover, the method of apply | coating and impregnating and drying the liquid which melt | dissolved or disperse | distributed said polymer solid electrolyte on the reinforcing material is also mentioned. Besides this method, impregnation can be performed by spraying or brushing, but any method may be used. Further, it is preferable that the excess polymer solid electrolyte adhering to the surface of the nonwoven fabric after impregnation is scraped off with a scraper, wiper, air knife, roller or the like to limit the amount of adhesion. The polymer solid electrolyte membrane separately prepared for the impregnated polymer solid electrolyte membrane prepared by such a method can be further combined by pressing under heating.
本発明の高分子固体電解質膜が塩基性重合体を添加物として含む場合には、上記の含浸液に塩基性重合体を通常の混合方法を用いて添加すれば構わない。一例をあげると高分子固体電解質が水、アルコール類等のプロトン溶媒や、ＤＭＦ（ジメチルホルムアミド）、ＤＭＡｃ（ジメチルアセトアミド）、ＤＭＳＯ（ジメチルスルホキサイド）、ＮＭＰ（Ｎ−メチル−２−ピロリドン）等の極性非プロトン溶媒、或いは、その混合溶媒に溶解あるいは分散した混合液と塩基性重合体がＤＭＦ，ＤＭＡｃ、ＤＭＳＯ，ＮＭＰ等の極性非プロトン溶媒に溶解あるいは分散した液を混ぜ合わせることにより塩基性重合体を添加物として含む高分子固体電解質の含浸液を得ることができる。
補強材の内部に高分子固体電解質あるいは塩基性重合体を添加物として含む高分子固体電解質を充填する際の含浸液の固形分濃度は内部に十分に充填することを考えると５質量％以上であることが望ましく、１０質量％以上であることがさらに望ましい。５質量％よりも濃度が小さい場合には空孔を完全に埋めることができない。含浸後になお空孔を有する場合には繰り返し含浸することもできる。その際には含浸後に風乾または熱風等を十分に当てて溶剤を乾燥、除去した後に再度含浸をする。また含浸においては雰囲気を減圧にすることや超音波を照射した場合に好適に空孔を残さずに含浸が達成されるが必ずしも減圧や超音波は必要ではない。
When the solid polymer electrolyte membrane of the present invention contains a basic polymer as an additive, the basic polymer may be added to the above impregnating solution using a normal mixing method. For example, the solid polymer electrolyte is a proton solvent such as water or alcohol, DMF (dimethylformamide), DMAc (dimethylacetamide), DMSO (dimethylsulfoxide), NMP (N-methyl-2-pyrrolidone), etc. By mixing a polar aprotic solvent or a mixed solution dissolved or dispersed in the mixed solvent with a liquid in which a basic polymer is dissolved or dispersed in a polar aprotic solvent such as DMF, DMAc, DMSO, or NMP. An impregnating solution of a solid polymer electrolyte containing a polymer as an additive can be obtained.
The solid content concentration of the impregnating liquid when filling the inside of the reinforcing material with the polymer solid electrolyte or the polymer solid electrolyte containing the basic polymer as an additive is 5% by mass or more considering that the inside is sufficiently filled. It is desirable that it is 10% by mass or more. When the concentration is less than 5% by mass, the vacancies cannot be completely filled. If there are pores after impregnation, the impregnation can be repeated. In that case, air impregnation or hot air is sufficiently applied after impregnation to dry and remove the solvent, and then impregnation again. Further, in the impregnation, when the atmosphere is reduced in pressure or when ultrasonic waves are irradiated, the impregnation is suitably achieved without leaving voids, but the reduced pressure and ultrasonic waves are not necessarily required.
上記のような方法で得られた補強材を有する高分子固体電解質膜は引き続き熱処理される事が望ましい。熱処理により補強材と高分子固体電解質が強固に密着され、その結果機械的強度が安定化される。熱処理温度は、好ましくは１２０℃以上３００℃以下、更に好ましくは１４０℃以上である２５０℃以下、最も好ましくは１６０℃以上２３０℃以下である。
熱処理温度が低いと補強材と高分子固体電解質間の密着力が確保できず好ましくない。この場合８０℃程度の水に浸漬すると含浸した高分子固体電解質が溶け出してくることがある。一方、熱処理温度が高いと高分子固体電解質、塩基性重合体等が変質する可能性があり好ましくない。熱処理の時間は、熱処理温度にもよるが、好ましくは５分以上３時間以下、更に好ましくは１０分以上２時間以下である。
含浸後に熱処理を施した高分子固体電解質膜は実質的に空気不透過である。空気の透過性の測定方法は後述する特性値の測定方法の欄に記載するが、この測定を行った際の透気度（ガーレー数）は５０００秒以上であることが好ましく、１００００秒以上であることがさらに好ましく、最も好ましくは２００００秒以上である。５０００秒未満の場合には全く実用に供さない。本発明の空気不透過とは５０００秒以上のことをいう。
It is desirable that the polymer solid electrolyte membrane having the reinforcing material obtained by the above method is subsequently heat treated. By heat treatment, the reinforcing material and the solid polymer electrolyte are firmly adhered, and as a result, the mechanical strength is stabilized. The heat treatment temperature is preferably 120 ° C. or higher and 300 ° C. or lower, more preferably 140 ° C. or higher and 250 ° C. or lower, most preferably 160 ° C. or higher and 230 ° C. or lower.
If the heat treatment temperature is low, the adhesion between the reinforcing material and the polymer solid electrolyte cannot be secured, which is not preferable. In this case, when immersed in water at about 80 ° C., the impregnated polymer solid electrolyte may melt out. On the other hand, if the heat treatment temperature is high, the solid polymer electrolyte, the basic polymer and the like may be altered, which is not preferable. Although the heat treatment time depends on the heat treatment temperature, it is preferably 5 minutes or longer and 3 hours or shorter, more preferably 10 minutes or longer and 2 hours or shorter.
The polymer solid electrolyte membrane subjected to heat treatment after impregnation is substantially impermeable to air. The air permeability measurement method is described in the column of the characteristic value measurement method described later. The air permeability (Gurley number) when this measurement is performed is preferably 5000 seconds or more, and preferably 10,000 seconds or more. More preferably, it is most preferably 20000 seconds or longer. When it is less than 5000 seconds, it is not used at all. The air impermeability of the present invention means 5000 seconds or more.
本発明の高分子固体電解質膜のイオン交換容量としては特に限定されないが、１ｇ当たり０．５０〜４．００ミリ当量が好ましく、より好ましくは０．８３〜４．００ミリ当量、最も好ましくは１．００〜１．５０ミリ当量である。より大きいイオン交換容量の高分子固体電解質膜を用いる方が、高温低加湿条件下においてより高いプロトン伝導性を示し、燃料電池に用いた場合、運転時により高い出力を得ることができる。
高分子固体電解質膜の乾燥時に対する含水時の寸法の変化は乾湿寸法変化の振幅の測定で評価される。測定方法は後述する特性値の測定方法の欄に記すが、乾湿寸法変化の振幅が１０％以下であることが好ましく、さらに好ましくは５％以下、最も好ましくは３％以下である。１０％以上の場合には生じる局所的なひずみが高分子固体電解質膜の劣化や破壊の基点となり長時間の連続運転には耐え得ない。
The ion exchange capacity of the polymer solid electrolyte membrane of the present invention is not particularly limited, but is preferably 0.50 to 4.00 milliequivalents per gram, more preferably 0.83 to 4.00 milliequivalents, and most preferably 1 0.001 to 1.50 milliequivalents. The use of a polymer solid electrolyte membrane having a larger ion exchange capacity exhibits higher proton conductivity under high temperature and low humidification conditions, and when used in a fuel cell, a higher output can be obtained during operation.
The change in the dimension of the polymer solid electrolyte membrane during drying with respect to the time of drying is evaluated by measuring the amplitude of the wet and dry dimensional change. Although the measurement method is described in the column of the characteristic value measurement method described later, the amplitude of the wet and dry dimensional change is preferably 10% or less, more preferably 5% or less, and most preferably 3% or less. In the case of 10% or more, the local strain generated becomes the starting point of deterioration or destruction of the polymer solid electrolyte membrane, and cannot withstand continuous operation for a long time.
本発明の高分子固体電解質膜を固体高分子形燃料電池に用いる場合、本発明の高分子固体電解質膜がアノードとカソードの間に密着保持されてなる膜／電極接合体（membrane/electrodeassembly）（以下、しばしば「ＭＥＡ」と称する）として使用される。ここでアノードはアノード触媒層からなり、プロトン伝導性を有し、カソードはカソード触媒層からなり、プロトン伝導性を有する。また、アノード触媒層とカソード触媒層のそれぞれの外側表面にガス拡散層（後述する）を接合したものもＭＥＡと呼ぶ。
アノード触媒層は、燃料（例えば水素）を酸化して容易にプロトンを生ぜしめる触媒を包含し、カソード触媒層は、プロトン及び電子と酸化剤（例えば酸素や空気）を反応させて水を生成させる触媒を包含する。アノードとカソードのいずれについても、触媒としては白金もしくは白金とルテニウム等を合金化した触媒が好適に用いられ、１０〜１０００オングストローム以下の触媒粒子であることが好ましい。また、このような触媒粒子は、ファーネスブラック、チャンネルブラック、アセチレンブラック、カーボンブラック、活性炭、黒鉛といった０．０１〜１０μｍ程度の大きさの導電性粒子に担持されていることが好ましい。触媒層投影面積に対する触媒粒子の担持量は、０．００１ｍｇ／ｃｍ２〜１０ｍｇ／ｃｍ２以下であることが好ましい。
さらにアノード触媒層とカソード触媒層は、パーフルオロカーボンスルホン酸ポリマーを含有することが好ましい。触媒層投影面積に対する担持量として、０．００１ｍｇ／ｃｍ２〜１０ｍｇ／ｃｍ２以下であることが好ましい。
When the polymer solid electrolyte membrane of the present invention is used in a polymer electrolyte fuel cell, a membrane / electrode assembly (membrane / electrode assembly) in which the polymer solid electrolyte membrane of the present invention is held tightly between an anode and a cathode ( Hereinafter often referred to as "MEA"). Here, the anode is composed of an anode catalyst layer and has proton conductivity, and the cathode is composed of a cathode catalyst layer and has proton conductivity. Further, a gas diffusion layer (described later) joined to the outer surface of each of the anode catalyst layer and the cathode catalyst layer is also referred to as MEA.
The anode catalyst layer includes a catalyst that easily oxidizes fuel (for example, hydrogen) to easily generate protons, and the cathode catalyst layer reacts protons and electrons with an oxidizing agent (for example, oxygen or air) to generate water. Includes catalyst. For both the anode and the cathode, platinum or a catalyst in which platinum and ruthenium are alloyed is preferably used as the catalyst, and the catalyst particles are preferably 10 to 1000 angstroms or less. Such catalyst particles are preferably supported on conductive particles having a size of about 0.01 to 10 μm such as furnace black, channel black, acetylene black, carbon black, activated carbon, and graphite. The amount of catalyst particles supported relative to the projected area of the catalyst layer is preferably 0.001 mg / cm 2 to 10 mg / cm 2 or less.
Furthermore, the anode catalyst layer and the cathode catalyst layer preferably contain a perfluorocarbon sulfonic acid polymer. The supported amount relative to the projected area of the catalyst layer is preferably 0.001 mg / cm 2 to 10 mg / cm 2 or less.
ＭＥＡの作製方法としては、例えば、次のような方法が挙げられる。まず、パーフルオロカーボンスルホン酸ポリマーをアルコールと水の混合溶液に溶解したものに、触媒として市販の白金担持カーボン（例えば、田中貴金属（株）製ＴＥＣ１０Ｅ４０Ｅ）を分散させてペースト状にする。これを２枚のＰＴＦＥシートのそれぞれの片面に一定量塗布して乾燥させて触媒層を形成する。次に、各ＰＴＦＥシートの塗布面を向かい合わせにして、その間に本発明の高分子固体電解質膜を挟み込み、１００〜２００℃で熱プレスにより転写接合してから、ＰＴＦＥシートを取り除くことにより、ＭＥＡを得ることができる。
当業者にはＭＥＡの作製方法は周知である。ＭＥＡの作製方法は、例えば、ＪＯＵＲＮＡＬ ＯＦ ＡＰＰＬＩＥＤ ＥＬＥＣＴＲＯＣＨＥＭＩＳＴＲＹ，２２（１９９２）ｐ．１−７に詳しく記載されている。
As a method for manufacturing the MEA, for example, the following method can be given. First, commercially available platinum-supported carbon (for example, TEC10E40E manufactured by Tanaka Kikinzoku Co., Ltd.) as a catalyst is dispersed in a solution in which a perfluorocarbon sulfonic acid polymer is dissolved in a mixed solution of alcohol and water to form a paste. A certain amount of this is applied to one side of each of the two PTFE sheets and dried to form a catalyst layer. Next, the coated surfaces of the PTFE sheets are faced to each other, the polymer solid electrolyte membrane of the present invention is sandwiched between them, and transferred and bonded by hot pressing at 100 to 200 ° C., and then the PTFE sheet is removed, thereby removing the MEA. Can be obtained.
A person skilled in the art knows how to make MEAs. The method for producing MEA is described in, for example, JOURNAL OF APPLIED ELECTROCHEMISTRY, 22 (1992) p. 1-7.
ガス拡散層としては、市販のカーボンクロスもしくはカーボンペーパーを用いることができる。前者の代表例としては、米国ＤＥ ＮＯＲＡ ＮＯＲＴＨ ＡＭＥＲＩＣＡ社製カーボンクロスＥ−ｔｅｋ，Ｂ−１が挙げられ、後者の代表例としては、ＣＡＲＢＥＬ（登録商標、ジャパンゴアテックス（株））、東レ（株）製ＴＧＰ−Ｈ、米国ＳＰＣＴＲＡＣＯＲＰ社製カーボンペーパー２０５０等が挙げられる。また、電極触媒層とガス拡散層が一体化した構造体は「ガス拡散電極」と呼ばれる。ガス拡散電極を本発明の高分子固体電解質膜に接合してもＭＥＡが得られる。市販のガス拡散電極の代表例としては、米国ＤＥ ＮＯＲＡ ＮＯＲＴＨ ＡＭＥＲＩＣＡ社製ガス拡散電極ＥＬＡＴ（登録商標）（ガス拡散層としてカーボンクロスを使用）が挙げられる。
上記ＭＥＡのアノードとカソードを高分子固体電解質膜の外側に位置する電子伝導性材料を介して互いに結合させると、作動可能な固体高分子形燃料電池を得ることができる。当業者には固体高分子形燃料電池の作成方法は周知である。固体高分子形燃料電池の作成方法は、例えば、ＦＵＥＬ ＣＥＬＬ ＨＡＮＤＢＯＯＫ（ＶＡＮ ＮＯＳＴＲＡＮＤ ＲＥＩＮＨＯＬＤ、Ａ．Ｊ．ＡＰＰＬＥＢＹ ｅｔ．ａｌ、ＩＳＢＮ ０−４４２−３１
９２６−６）、化学Ｏｎｅ Ｐｏｉｎｔ，燃料電池（第二版），谷口雅夫，妹尾学編，共立出版（１９９２）等に詳しく記載されている。
A commercially available carbon cloth or carbon paper can be used as the gas diffusion layer. Representative examples of the former include carbon cloth E-tek, B-1 manufactured by DE NORA NORTH AMERICA, USA. Representative examples of the latter include CARBEL (registered trademark, Japan Gore-Tex Co., Ltd.), Toray Industries, Inc. ) Manufactured by TGP-H, carbon paper 2050 manufactured by SPCTRACORP, USA, and the like. A structure in which the electrode catalyst layer and the gas diffusion layer are integrated is called a “gas diffusion electrode”. MEA can also be obtained by joining the gas diffusion electrode to the solid polymer electrolyte membrane of the present invention. A typical example of a commercially available gas diffusion electrode is a gas diffusion electrode ELAT (registered trademark) manufactured by DE NORA NORTH AMERICA (using carbon cloth as a gas diffusion layer).
When the anode and cathode of the MEA are coupled to each other via an electron conductive material located outside the polymer solid electrolyte membrane, an operable polymer electrolyte fuel cell can be obtained. A person skilled in the art knows how to make a polymer electrolyte fuel cell. A method for producing a polymer electrolyte fuel cell is, for example, FUEL CELL HANDBOOK (VAN NOSTRAND REINHOLD, AJ APPLEBY et.al, ISBN 0-442-31).
926-6), Chemistry One Point, Fuel Cell (Second Edition), Masao Taniguchi, Manabu Seneo, Kyoritsu Shuppan (1992) and the like.
電子伝導性材料としては、その表面に燃料や酸化剤等のガスを流すための溝を形成させたグラファイトまたは樹脂との複合材料、金属製のプレート等の集電体を用いる。上記ＭＥＡがガス拡散層を有さない場合、ＭＥＡのアノードとカソードのそれぞれの外側表面にガス拡散層を位置させた状態で単セル用ケーシング（例えば、米国エレクトロケム社製 ＰＥＦＣ単セル）に組み込むことにより固体高分子形燃料電池が得られる。
高電圧を取り出すためには、上記のような単セルを複数積み重ねたスタックセルとして燃料電池を作動させる。このようなスタックセルとしての燃料電池を作成するためには、複数のＭＥＡを作成してスタックセル用ケーシング（例えば、米国エレクトロケム社製 ＰＥＦＣスタックセル）に組み込む。このようなスタックセルとしての燃料電池においては、隣り合うセルの燃料と酸化剤を分離する役割と隣り合うセル間の電気的コネクターの役割を果たすバイポーラプレートと呼ばれる集電体が用いられる。
燃料電池の運転は、一方の電極に水素を、他方の電極に酸素または空気を供給することによって行われる。燃料電池の作動温度は高温であるほど触媒活性が上がるために好ましい。通常は、水分管理が容易な５０〜８０℃で作動させることが多いが、８０℃〜１５０℃で作動させることもできる。
As the electron conductive material, a current collector such as a composite material of graphite or resin having a groove for flowing a gas such as fuel or oxidant on its surface, or a metal plate is used. When the MEA does not have a gas diffusion layer, the MEA is incorporated into a single cell casing (for example, PEFC single cell manufactured by Electrochem Inc., USA) with the gas diffusion layer positioned on the outer surface of each anode and cathode of the MEA. Thus, a polymer electrolyte fuel cell can be obtained.
In order to extract a high voltage, the fuel cell is operated as a stack cell in which a plurality of single cells as described above are stacked. In order to produce such a fuel cell as a stack cell, a plurality of MEAs are produced and assembled into a stack cell casing (for example, PEFC stack cell manufactured by US Electrochem Corp.). In such a fuel cell as a stack cell, a current collector called a bipolar plate is used which serves to separate the fuel and oxidant of adjacent cells and to serve as an electrical connector between the adjacent cells.
The fuel cell is operated by supplying hydrogen to one electrode and oxygen or air to the other electrode. The higher the operating temperature of the fuel cell, the higher the catalyst activity. Usually, it is often operated at 50 to 80 ° C., where moisture management is easy, but it can also be operated at 80 to 150 ° C.
以下に実施例に基づいて本発明をさらに具体的に説明する。
（特性値の測定方法）
（１）イオン交換容量
まず、１０ｃｍ２程度に切り出した（複合）高分子電解質膜を１１０℃にて真空乾燥して、乾燥重量Ｗ（ｇ）を求める。この膜を５０ｍｌの２５℃飽和ＮａＣｌ水溶液に浸漬してＨ＋を遊離させ、フェノールフタレインを指示薬として、０．０１Ｎ水酸化ナトリウム水溶液で中和滴定を行い、中和に要したＮａＯＨの等量Ｍ（ミリ等量）を求める。このようにして求めたＭをＷで割って得られる値がイオン交換容量（ミリ等量／ｇ）である。また、ＷをＭで割って１０００倍した値が当量質量ＥＷであり、イオン交換基１当量当りの乾燥質量グラム数である。
（２）膜厚
高分子固体電解質膜を２３℃、６５％の恒温室で１２時間以上放置した後に、東洋精機製作所製Ｂ−１型膜膜厚計を用いて測定した。
Hereinafter, the present invention will be described more specifically based on examples.
(Measurement method of characteristic value)
(1) Ion exchange capacity First, the (composite) polymer electrolyte membrane cut out to about 10 cm 2 is vacuum-dried at 110 ° C. to determine the dry weight W (g). This membrane is immersed in 50 ml of a saturated NaCl aqueous solution at 25 ° C. to release H + , and neutralization titration is performed with 0.01 N sodium hydroxide aqueous solution using phenolphthalein as an indicator, and the equivalent amount of NaOH required for neutralization. Obtain M (millimeter equivalent). The value obtained by dividing M thus determined by W is the ion exchange capacity (milli equivalent / g). The value obtained by dividing W by M and multiplying by 1000 is the equivalent mass EW, which is the dry mass in grams per equivalent of ion-exchange groups.
(2) Film thickness After the polymer solid electrolyte membrane was allowed to stand for 12 hours or more in a thermostatic chamber at 23 ° C. and 65%, it was measured using a B-1 type film thickness meter manufactured by Toyo Seiki Seisakusho.
（３）乾湿寸法変化の振幅
高分子固体電解質膜を２３℃・５０％の恒温室で1時間以上放置したあと、任意のサイズに切り出し、初期の寸法（縦方向の長さＡ（ｃｍ）、横方向の長さＢ（ｃｍ））を測定した。そのサンプルを８０℃熱水に１時間浸漬させ、膨潤時の寸法（縦方向の長さＣ（ｃｍ）、横方向の長さＤ（ｃｍ））を測定し、下記式を用いて８０℃での縦方向、横方向それぞれの膨潤寸法変化率を求め、その平均を膨潤寸法変化率△Ｗ（％）とした。
△Ｗ縦＝（（Ｃ−Ａ）／Ａ）×１００
△Ｗ横＝（（Ｄ−Ｂ）／Ｂ）×１００
△Ｗ＝（△Ｗ縦＋△Ｗ横）／２
引き続き、膨潤したサンプルを２３℃・５０％の恒温室で１時間以上放置、乾燥させ、乾燥時の寸法（縦方向の長さＥ（ｃｍ）、横方向の長さＦ（ｃｍ））を測定し、下記式を用いて乾燥時での縦方向、横方向それぞれの乾燥寸法変化率を求め、その平均を乾燥寸法変化率△Ｋ（％）とした。
△Ｋ縦＝（（Ｅ−Ａ）／Ａ）×１００
△Ｋ横＝（（Ｆ−Ｂ）／Ｂ）×１００
△Ｋ＝（△Ｋ縦＋△Ｋ横）／２
これらより、以下の式を用いて繰り返し乾湿寸法変化の振幅△Ｈ（％）を求めた。
△Ｈ＝△Ｗ−△Ｋ
(3) Amplitude of wet and dry dimensional change After leaving the polymer solid electrolyte membrane in a constant temperature room at 23 ° C. and 50% for 1 hour or longer, cut it out to an arbitrary size and set the initial dimensions (length A (cm) in the vertical direction, The lateral length B (cm)) was measured. The sample was immersed in hot water at 80 ° C. for 1 hour, and the dimensions at the time of swelling (longitudinal length C (cm), lateral length D (cm)) were measured. The swelling dimensional change rate in each of the vertical direction and the horizontal direction was determined, and the average was defined as the swelling dimensional change rate ΔW (%).
ΔW length = ((C−A) / A) × 100
ΔW width = ((D−B) / B) × 100
△ W = (△ W length + △ W width ) / 2
Subsequently, the swollen sample was allowed to stand in a thermostatic chamber at 23 ° C. and 50% for 1 hour or more and dried, and the dimensions during drying (longitudinal length E (cm), lateral length F (cm)) were measured. Then, the dry dimensional change rates in the vertical and horizontal directions during drying were determined using the following formula, and the average was defined as the dry dimensional change rate ΔK (%).
ΔK length = ((EA) / A) × 100
ΔK horizontal = ((F−B) / B) × 100
△ K = (△ K vertical + △ K horizontal ) / 2
From these, the amplitude ΔH (%) of the wet and dry dimensional change was repeatedly determined using the following equation.
△ H = △ W- △ K
（４）プロトン伝導度
高分子固体電解質膜を８０℃の湯中で処理した後に、膨潤状態のまま幅１ｃｍ、長さ７ｃｍに切出し、厚みT を測定した。このサンプルを膨潤状態のまま伝導度を測定する２端子式の伝導度測定セルに装着した。このセルを８０℃のイオン交換水中に浸漬し、交流インピーダンス法により周波数１０ｋHzにおける抵抗値Rを測定し、以下の式からプロトン伝導度σを算出した。
σ＝L ／（R ×T ×W ）
σ：プロトン伝導度（S/cm）
T ：厚み（ｃｍ）
R ：抵抗値（Ω）
L ：２端子間距離（＝５ｃｍ）
W ：サンプル幅（＝１ｃｍ）
(4) Proton conductivity After the polymer solid electrolyte membrane was treated in hot water at 80 ° C., it was cut into a 1 cm width and a 7 cm length in a swollen state, and the thickness T was measured. This sample was attached to a two-terminal conductivity measuring cell for measuring conductivity in a swollen state. This cell was immersed in ion exchange water at 80 ° C., a resistance value R at a frequency of 10 kHz was measured by an alternating current impedance method, and proton conductivity σ was calculated from the following equation.
σ = L / (R × T × W)
σ: Proton conductivity (S / cm)
T: Thickness (cm)
R: Resistance value (Ω)
L: Distance between two terminals (= 5cm)
W: Sample width (= 1 cm)
（５）燃料電池膜としての耐久性時間
Ｎａｆｉｏｎ溶液（アルドリッチ社製、Ｎａｆｉｏｎ固形分１０％、溶媒 水／エタノール重量比＝１／１に、触媒として市販の白金担持カーボン（田中貴金属（株）社製ＴＥＣ１０Ｅ４０Ｅ）を分散させてペースト状にする。これを２枚のＰＴＦＥシートのそれぞれの片面に０．８ｍｇ／ｃｍ２して乾燥させて触媒層を形成した。次に、各ＰＴＦＥシートの塗布面を向かい合わせにして、その間に本発明の高分子固体電解質膜を挟み込み、１５０℃、圧力５ＭＰａで９０秒間プレスしてＭＥＡを作成した。
得られたＭＥＡの両側にガス拡散層としてカーボンクロスをセットして燃料電池単セル評価装置に組み込み、水素ガスと空気を用いて０．１５ＭＰａ加圧下９５℃で燃料電池特性試験を行った。アノードとカソードのガスの加湿温度は６０℃とし、電流密度０．３Ａ／ｃｍ２で発電した。耐久性試験において、高分子電解質膜にピンホールが生じると、水素ガスがカソード側へ多量にリークする。このリーク量を調べ、測定値が著しく上昇した時点で試験終了とした。
(5) Durability time as fuel cell membrane Nafion solution (manufactured by Aldrich, Nafion solid content 10%, solvent water / ethanol weight ratio = 1/1, commercially available platinum-supported carbon (Tanaka Kikinzoku Co., Ltd.) TEC10E40E) was dispersed into a paste, which was dried on each side of each of the two PTFE sheets by 0.8 mg / cm 2 to form a catalyst layer. The polymer solid electrolyte membrane of the present invention was sandwiched therebetween and pressed at 150 ° C. and a pressure of 5 MPa for 90 seconds to prepare an MEA.
A carbon cloth was set as a gas diffusion layer on both sides of the obtained MEA and incorporated in a fuel cell single cell evaluation apparatus, and a fuel cell characteristic test was conducted at 95 ° C. under a pressure of 0.15 MPa using hydrogen gas and air. The humidification temperature of the anode and cathode gases was 60 ° C., and power was generated at a current density of 0.3 A / cm 2 . In the durability test, when a pinhole is generated in the polymer electrolyte membrane, a large amount of hydrogen gas leaks to the cathode side. The amount of leak was examined, and the test was terminated when the measured value increased significantly.
（６）透気度
ＪＩＳ Ｐ８１１７に基づき、ガーレ式デンソメータ（島津社製）を用い、空気１００ｃｃが透過する時間（秒）を透気度（ガーレー値）として計測し、連続孔の有無を判断した。測定は５サンプルについて行い、その平均値を求めた。なお、連続孔が存在しない場合、透気度は無限大になる。
（７）破断強度
ＪＩＳ Ｋ７１１３に基づき、島津製作所製精密万能試験機ＡＧＳ−１ＫＮＧを用いて高分子固体電解質膜の破断強度を測定した。サンプルは２３℃、６５％の恒温室で１２時間以上放置した後に幅５ｍｍ、長さ５０ｍｍに切出し測定に供した。測定は３サンプルについて行い、その平均値を求めた。
(6) Air permeability Based on JIS P8117, using a Gurley type densometer (manufactured by Shimadzu Corporation), the time (seconds) through which 100 cc of air passes was measured as the air permeability (Gurley value), and the presence or absence of continuous holes was judged. . The measurement was performed on 5 samples, and the average value was obtained. In addition, when there is no continuous hole, the air permeability becomes infinite.
(7) Breaking strength Based on JIS K7113, the breaking strength of the solid polymer electrolyte membrane was measured using a precision universal testing machine AGS-1KNG manufactured by Shimadzu Corporation. The sample was left to stand for 12 hours or more in a thermostatic chamber at 23 ° C. and 65%, and then cut out to a width of 5 mm and a length of 50 mm and subjected to measurement. Measurement was performed on three samples, and the average value was obtained.
（８）不織布の空孔率
不織布を１０ｃｍ×１０ｃｍの大きさに切断し２３℃５０％の恒温室で２４時間以上放置した後に重量測定を行った。また特性値の測定方法（２）に示した方法で膜圧を測定した。重量Ｗ（ｇ）、膜厚ｄ（μｍ）、液晶ポリエステルの比重をｘ（ｇ／ｃｍ３）として
空孔率（％）＝１００−［Ｗ／（１０×１０×ｄ×１０−４×ｘ）］
として算出した。液晶ポリエステルの比重は１．４０ｇ／ｃｍ３として計算した。
(8) Porosity of nonwoven fabric The nonwoven fabric was cut into a size of 10 cm x 10 cm and left standing in a temperature-controlled room at 23 ° C and 50% for 24 hours or more, and then the weight was measured. Further, the membrane pressure was measured by the method shown in the characteristic value measurement method (2). Porosity (%) = 100− [W / (10 × 10 × d × 10 −4 × x) where weight W (g), film thickness d (μm), and specific gravity of liquid crystal polyester is x (g / cm 3 ). ]]
Calculated as The specific gravity of the liquid crystal polyester was calculated as 1.40 g / cm 3 .
（参考例１）フッ素系高分子固体電解質溶液の作成法
フッ素系高分子固体電解質として、［CF２CF２］０．８１２−［CF２−CF（−O−（CF２）２−SO３H）］０．１８８で表されるパーフルオロカーボンスルホン酸ポリマー（以下、「ＰＦＳ」と称する）を用いて、ＰＦＳ／ＰＢＩ＝１００／１（質量比）の塩基性重合体を含むフッ素系高分子固体電解質溶液（含浸液Ｄ）を以下のように製造した。
重量平均分子量が２７０００であるポリ［２，２’−（ｍ−フェニレン）−５，５’−ビベンズイミダゾール］（シグマアルドリッチジャパン（株）製、以下ＰＢＩと称する）をＮ，Ｎ−ジメチルアセトアミド（以下、「ＤＭＡＣ」と称する）とともにオートクレーブ中に入れて密閉し、２００℃まで昇温して５時間保持した。その後、オートクレーブを自然冷却して、ＰＢＩ／ＤＭＡＣ＝１０／９０（質量％）の組成のＰＢＩ溶液を得た。このＰＢＩ溶液の固有粘度は０．８（ｄｌ／ｇ）であった。さらに、このＰＢＩ溶液をＤＭＡＣで１０倍に希釈して、ＰＢＩ／ＤＭＡＣ＝１／９９（質量％）の組成の前段階溶液Ａを作製した。
Reference Example 1 Preparation Method of Fluorine Polymer Solid Electrolyte Solution As a fluorine polymer solid electrolyte, [CF 2 CF 2 ] 0.812- [CF 2 -CF (-O- (CF 2 ) 2 -SO 3 H)] A fluoropolymer containing a basic polymer of PFS / PBI = 100/1 (mass ratio) using a perfluorocarbon sulfonic acid polymer represented by 0.188 (hereinafter referred to as “PFS”). A solid electrolyte solution (impregnation liquid D) was produced as follows.
Poly [2,2 ′-(m-phenylene) -5,5′-bibenzimidazole] having a weight average molecular weight of 27000 (manufactured by Sigma-Aldrich Japan Co., Ltd., hereinafter referred to as PBI) is N, N-dimethylacetamide. (Hereinafter referred to as “DMAC”) and sealed in an autoclave, heated to 200 ° C. and held for 5 hours. Thereafter, the autoclave was naturally cooled to obtain a PBI solution having a composition of PBI / DMAC = 10/90 (mass%). The intrinsic viscosity of this PBI solution was 0.8 (dl / g). Further, this PBI solution was diluted 10 times with DMAC to prepare a pre-stage solution A having a composition of PBI / DMAC = 1/99 (mass%).
次に、テトラフルオロエチレンとCF２＝CFO（CF２）２−SO２Fとのパーフルオロカーボン重合体を製造した。得られたポリマーを、水酸化カリウム（１５質量％）とジメチルスルホキシド（３０質量％）を溶解した水溶液中に、６０℃で４時間接触させて、加水分解処理を行った。その後、６０℃水中に４時間浸漬した。次に６０℃の２Ｎ塩酸水溶液に３時間浸漬した後、イオン交換水で水洗、乾燥することで、イオン交換容量１．４１ミリ当量／ｇのＰＦＳを得た。
このＰＦＳをエタノール水溶液（水：エタノール＝５０．０：５０．０（質量比））とともにオートクレーブ中に入れて密閉し、１８０℃まで昇温して５時間保持した。その後、オートクレーブを自然冷却して、ＰＦＳ：水：エタノール＝５．０：４７．５：４７．５（質量％）の組成のポリマー溶液を得た。このポリマー溶液をエバポレータで減圧濃縮を行った後、水を添加してＰＦＳ／水＝８．５／９１．５（質量比）溶液を前段階溶液Ｂとして製造した。
Next, a perfluorocarbon polymer of tetrafluoroethylene and CF 2 ═CFO (CF 2 ) 2 —SO 2 F was produced. The obtained polymer was subjected to hydrolysis treatment by bringing it into contact with an aqueous solution in which potassium hydroxide (15% by mass) and dimethyl sulfoxide (30% by mass) were dissolved at 60 ° C. for 4 hours. Then, it was immersed in 60 degreeC water for 4 hours. Next, it was immersed in a 2N aqueous hydrochloric acid solution at 60 ° C. for 3 hours, then washed with ion-exchanged water and dried to obtain PFS having an ion-exchange capacity of 1.41 meq / g.
This PFS was placed in an autoclave together with an aqueous ethanol solution (water: ethanol = 50.0: 50.0 (mass ratio)), sealed, heated to 180 ° C. and held for 5 hours. Thereafter, the autoclave was naturally cooled to obtain a polymer solution having a composition of PFS: water: ethanol = 5.0: 47.5: 47.5 (mass%). This polymer solution was concentrated under reduced pressure using an evaporator, and then water was added to prepare a PFS / water = 8.5 / 91.5 (mass ratio) solution as the pre-stage solution B.
得られた前段階溶液ＢにＤＭＡＣを添加し、１２０℃で１時間還流した後、エバポレータで減圧濃縮を行って、ＰＦＳ／ＤＭＡＣ＝１．５／９８．５（質量比）溶液を前段階溶液Ｃとして製造した。
次に４０．０ｇの前段階溶液Ｃに６．５ｇの前段階溶液Ａを添加し混合した後、６８．９ｇの前段階溶液Ｂを加えて攪拌し、さらに８０℃にて減圧濃縮して含浸液Ｄを得た。この含浸液中のＰＦＳとＰＢＩの濃度は、各々５．６００質量％と０．０５６質量％であった。
［実施例１］
After adding DMAC to the obtained pre-stage solution B and refluxing at 120 ° C. for 1 hour, the solution was concentrated under reduced pressure with an evaporator to obtain a PFS / DMAC = 1.5 / 98.5 (mass ratio) solution. Manufactured as C.
Next, after adding 6.5 g of the pre-stage solution A to 40.0 g of the pre-stage solution C and mixing, 68.9 g of the pre-stage solution B is added and stirred, and further concentrated under reduced pressure at 80 ° C. Liquid D was obtained. The concentrations of PFS and PBI in this impregnation liquid were 5.600 mass% and 0.056 mass%, respectively.
[Example 1]
一般式（３）で表される芳香族液晶ポリエステルのうちｍ＝０．７５，ｎ＝０．２５である構造を有する不織布（膜厚２０μｍ、空孔率８３％）を参考例１で調整した前段階溶液Ｂに浸漬し次いで８０℃の熱風下で１０分間乾燥するという操作を３回繰り返して芳香族液晶ポリエステル不織布内に高分子固体電解質を含浸した。含浸後に２００℃の熱風下に１時間おき、完全に溶媒を飛ばし複合固体高分子電解質膜を得た。得られた複合固体高分子電解質膜は２Ｎの塩酸で８時間洗浄し、次いで純水で濯ぎ４０μｍの高分子固体電解質膜を得た。この膜の評価結果を表１に示すが良好な乾湿寸法変化特性、機械特性を示し、また良好な燃料電池膜としての耐久性を示した。
［実施例２］
A non-woven fabric (film thickness 20 μm, porosity 83%) having a structure of m = 0.75 and n = 0.25 of the aromatic liquid crystal polyester represented by the general formula (3) was prepared in Reference Example 1. The operation of immersing in the pre-stage solution B and then drying for 10 minutes under hot air at 80 ° C. was repeated three times to impregnate the polymer liquid electrolyte in the aromatic liquid crystal polyester nonwoven fabric. After the impregnation, the composite solid polymer electrolyte membrane was obtained by leaving the solvent completely for 1 hour under hot air at 200 ° C. to completely remove the solvent. The obtained composite solid polymer electrolyte membrane was washed with 2N hydrochloric acid for 8 hours and then rinsed with pure water to obtain a 40 μm polymer solid electrolyte membrane. The evaluation results of this membrane are shown in Table 1. The membrane showed good wet / dry dimensional change characteristics and mechanical properties, and also showed good durability as a fuel cell membrane.
[Example 2]
一般式（３）で表される芳香族液晶ポリエステルのうちｍ＝０．７５，ｎ＝０．２５である構造を有する不織布（膜厚２０μｍ、空孔率８３％）を参考例１で調整した含浸液Ｄに浸漬し次いで８０℃の熱風下で１０分間乾燥するという操作を２回繰り返して全芳香族液晶ポリエステル不織布内にイオン交換樹脂を含浸した。含浸後に２００℃の熱風下に１時間おき、完全に溶媒を飛ばし高分子固体電解質膜を得た。得られた高分子固体電解質膜は２Ｎの塩酸で８時間洗浄し、次いで純水で濯ぎ４０μｍの高分子固体電解質膜を得た。この膜の評価結果を表１に示すが良好な乾湿寸法変化特性、機械特性を示し、また良好な燃料電池膜としての耐久性を示した。
［実施例３］
A non-woven fabric (film thickness 20 μm, porosity 83%) having a structure of m = 0.75 and n = 0.25 of the aromatic liquid crystal polyester represented by the general formula (3) was prepared in Reference Example 1. The operation of dipping in the impregnating solution D and then drying for 10 minutes under hot air at 80 ° C. was repeated twice to impregnate the wholly aromatic liquid crystal polyester nonwoven fabric with the ion exchange resin. After impregnation, the polymer solid electrolyte membrane was obtained by leaving the solvent completely for 1 hour under hot air at 200 ° C. The obtained polymer solid electrolyte membrane was washed with 2N hydrochloric acid for 8 hours and then rinsed with pure water to obtain a polymer solid electrolyte membrane of 40 μm. The evaluation results of this membrane are shown in Table 1. The membrane showed good wet / dry dimensional change characteristics and mechanical properties, and also showed good durability as a fuel cell membrane.
[Example 3]
一般式（３）で表される芳香族液晶ポリエステルのうちｍ＝０．７５，ｎ＝０．２５である構造を有する不織布（膜厚３０μｍ、空孔率８３％）を使用した以外は実施例１と同様に実施した。この膜の評価結果を表１に示すが良好な乾湿寸法変化特性、機械特性を示し、また良好な燃料電池膜としての耐久性を示した。
［実施例４］
Example using the non-woven fabric (film thickness 30 μm, porosity 83%) having a structure of m = 0.75 and n = 0.25 among the aromatic liquid crystalline polyester represented by the general formula (3) 1 was carried out. The evaluation results of this membrane are shown in Table 1. The membrane showed good dry / wet dimensional change characteristics and mechanical properties, and also showed good durability as a fuel cell membrane.
[Example 4]
参考例１で作成した含浸液Ｄをガラスシャーレに展開し６０℃、次いで８０℃のホットプレート上で各１時間溶媒を揮散させることにより膜厚５μｍの補強材を含まない電解質膜を得た。実施例１で得た高分子固体電解質膜の両表面をこの補強材を含まない電解質膜ではさみ、加熱下でプレスし一体化させた。プレス条件は真空下１９０℃、６０ｋｇ／ｃｍ２で３０分であった。得られた高分子固体電解質膜は２Ｎの塩酸で８時間洗浄し、次いで純水で濯ぎ５０μｍの高分子固体電解質膜２を得た。
この膜の評価結果を表１に示すが良好な乾湿寸法変化特性、機械特性を示し、また良好な燃料電池膜としての耐久性を示した。
［比較例１］
The impregnating solution D prepared in Reference Example 1 was spread on a glass petri dish, and the solvent was evaporated on a hot plate at 60 ° C. and then at 80 ° C. for 1 hour to obtain an electrolyte membrane containing no reinforcing material with a thickness of 5 μm. Both surfaces of the polymer solid electrolyte membrane obtained in Example 1 were sandwiched between electrolyte membranes not containing this reinforcing material, and pressed and integrated under heating. The press conditions were 190 ° C. under vacuum and 60 kg / cm 2 for 30 minutes. The obtained solid polymer electrolyte membrane was washed with 2N hydrochloric acid for 8 hours and then rinsed with pure water to obtain a solid polymer electrolyte membrane 2 having a thickness of 50 μm.
The evaluation results of this membrane are shown in Table 1. The membrane showed good wet / dry dimensional change characteristics and mechanical properties, and also showed good durability as a fuel cell membrane.
[Comparative Example 1]
Ｎａｆｉｏｎ溶液（Ａｌｄｒｉｃｈ社製、５％、水溶液、ＥＷ＝１１００）をガラス製シャーレに流し込み、ホットプレート上で６０℃、次いで８０℃各１時間溶媒を揮散させ、さらに１６０℃の熱風乾燥機で１時間熱処理した。得られた高分子固体電解質膜は２Ｎの塩酸で８時間洗浄し、次いで純水で濯ぎ５０μｍの補強材を含まない電解質膜を得た。この膜の評価結果を表１に示すが乾湿寸法変化特性、機械特性ともに悪く、また９５℃での燃料電池膜としての評価時間は著しく短かった。
［比較例２］
A Nafion solution (Aldrich, 5%, aqueous solution, EW = 1100) was poured into a glass petri dish, and the solvent was stripped on a hot plate at 60 ° C. and then at 80 ° C. for 1 hour each, and further with a hot air dryer at 160 ° C. Heat treated for hours. The obtained polymer solid electrolyte membrane was washed with 2N hydrochloric acid for 8 hours and then rinsed with pure water to obtain an electrolyte membrane containing no 50 μm reinforcing material. The evaluation results of this membrane are shown in Table 1. Both the wet and dry dimensional change characteristics and the mechanical properties were poor, and the evaluation time as a fuel cell membrane at 95 ° C. was remarkably short.
[Comparative Example 2]
ポリエチレンシート（膜厚１５μｍ、空孔率４６％）を使用した以外は実施例１と同様に実施した。この膜の評価結果を表１に示すが乾湿寸法変化特性、機械特性ともに悪く、また９５℃での燃料電池膜としての評価時間は著しく短かった。 The same operation as in Example 1 was performed except that a polyethylene sheet (film thickness: 15 μm, porosity: 46%) was used. The evaluation results of this membrane are shown in Table 1. Both dry and wet dimensional change characteristics and mechanical properties were poor, and the evaluation time as a fuel cell membrane at 95 ° C. was remarkably short.
本発明は、高温耐久性の向上作用を示し、燃料電池用の高分子固体電解質膜として好適
である。
The present invention exhibits an effect of improving high temperature durability and is suitable as a polymer solid electrolyte membrane for a fuel cell.
Claims (7)
［CF２CF２］a−［CF２−CF(−O−CF２−CF(CF３））ｂ−O−（CF２）ｆ−SO３H）］ｇ（１）
（式中、０≦ａ＜１、０＜ｇ≦１，ａ＋ｇ＝１，０≦ｂ≦３、１≦ｆ≦８である。） 3. The solid polymer electrolyte membrane according to claim 1, wherein the solid polymer electrolyte is an ion exchange resin made of a perfluorocarbon sulfonic acid polymer represented by the following formula (1).
[CF 2 CF 2] a - [CF 2 -CF (-O-CF 2 -CF (CF 3)) b -O- (CF 2) f -SO 3 H)] g (1)
(Where 0 ≦ a <1, 0 <g ≦ 1, a + g = 1, 0 ≦ b ≦ 3, 1 ≦ f ≦ 8)
［CF２CF２］a−［CF２−CF(−O−CF２−CF(CF３））ｂ−O−（CF２）ｆ−SO３H）］ｇ (２)
（式中、０≦ａ＜１、０＜ｇ≦１，ａ＋ｇ＝１，０≦ｂ＜１、１≦ｆ≦８である。） The polymer solid electrolyte membrane according to claim 1 or 2, wherein the polymer solid electrolyte is an ion exchange resin made of a perfluorocarbon sulfonic acid polymer represented by the following formula (2).
[CF 2 CF 2] a - [CF 2 -CF (-O-CF 2 -CF (CF 3)) b -O- (CF 2) f -SO 3 H)] g (2)
(Where 0 ≦ a <1, 0 <g ≦ 1, a + g = 1, 0 ≦ b <1, 1 ≦ f ≦ 8)
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| JP2012525719A (en) * | 2009-05-01 | 2012-10-22 | スリーエム イノベイティブ プロパティズ カンパニー | Passive electrical goods |
| JP2014002934A (en) * | 2012-06-19 | 2014-01-09 | Kaneka Corp | Polymer electrolyte membrane and use thereof |
| WO2015080292A1 (en) * | 2013-11-29 | 2015-06-04 | 旭化成イーマテリアルズ株式会社 | Polymer electrolyte film |
| JPWO2019188960A1 (en) * | 2018-03-29 | 2021-03-11 | 東レ株式会社 | Composite electrolyte membrane |
| WO2022220186A1 (en) | 2021-04-15 | 2022-10-20 | 旭化成株式会社 | Solid electrolyte support and solid electrolyte sheet including same |
| WO2023002999A1 (en) * | 2021-07-20 | 2023-01-26 | Ａｇｃ株式会社 | Method for producing composite sheet, and composite sheet |
| WO2023002998A1 (en) * | 2021-07-20 | 2023-01-26 | Ａｇｃ株式会社 | Composite sheet and method for producing composite sheet |
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| WO2022220186A1 (en) | 2021-04-15 | 2022-10-20 | 旭化成株式会社 | Solid electrolyte support and solid electrolyte sheet including same |
| KR20230147169A (en) | 2021-04-15 | 2023-10-20 | 아사히 가세이 가부시키가이샤 | Support for solid electrolyte and solid electrolyte sheet containing the same |
| WO2023002999A1 (en) * | 2021-07-20 | 2023-01-26 | Ａｇｃ株式会社 | Method for producing composite sheet, and composite sheet |
| WO2023002998A1 (en) * | 2021-07-20 | 2023-01-26 | Ａｇｃ株式会社 | Composite sheet and method for producing composite sheet |
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