KR20240009841A - Novel highly durable crosslinked poly(aryl piperidinium) ionomer, an anion exchange membrane and method for preparing the same - Google Patents
Novel highly durable crosslinked poly(aryl piperidinium) ionomer, an anion exchange membrane and method for preparing the same Download PDFInfo
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- KR20240009841A KR20240009841A KR1020220126050A KR20220126050A KR20240009841A KR 20240009841 A KR20240009841 A KR 20240009841A KR 1020220126050 A KR1020220126050 A KR 1020220126050A KR 20220126050 A KR20220126050 A KR 20220126050A KR 20240009841 A KR20240009841 A KR 20240009841A
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- anion exchange
- cross
- exchange membrane
- piperidinium
- copolymer ionomer
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 87
- 229920000554 ionomer Polymers 0.000 title claims abstract description 66
- -1 poly(aryl piperidinium Chemical compound 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 57
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 239000000446 fuel Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000003377 acid catalyst Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- GKNWQHIXXANPTN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-N 0.000 claims description 2
- XBWQFDNGNOOMDZ-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F XBWQFDNGNOOMDZ-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims description 2
- 210000004185 liver Anatomy 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 230000008961 swelling Effects 0.000 abstract description 8
- 239000004793 Polystyrene Substances 0.000 abstract description 5
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 5
- 229920002223 polystyrene Polymers 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 8
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 1
- 241001272567 Hominoidea Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005013 aryl ether group Chemical group 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
본 발명은 고분자 골격 내 아릴 에테르 결합이 없으면서 반복단위 내 폴리스티렌 연결기에 의하여 가교된 피페리디늄 그룹이 도입된 가교 폴리(아릴 피페리디늄) 공중합체 이오노머에 관한 것으로, 화학적 안정성, 이온전도도, 기계적 물성, 치수안정성 및 내구성이 매우 우수하다.
또한, 상기 가교 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 제조되는 음이온교환막은 막의 과도한 팽윤을 억제하고, 기계적 물성, 알칼리 안정성 및 내구성이 크게 향상되며, 저습도 조건에서도 작동이 가능하여 알칼리 연료전지용 막 및 바인더, 수전해 장치, 이산화탄소 환원, 또는 산화-환원 플로우 전지에 응용할 수 있다.The present invention relates to a cross-linked poly(aryl piperidinium) copolymer ionomer in which piperidinium groups cross-linked by a polystyrene linker in the repeating unit are introduced without an aryl ether bond in the polymer backbone, and has excellent chemical stability, ionic conductivity, and mechanical properties. , Dimensional stability and durability are very excellent.
In addition, the anion exchange membrane manufactured from the cross-linked poly(aryl piperidinium) copolymer ionomer suppresses excessive swelling of the membrane, greatly improves mechanical properties, alkali stability and durability, and can operate even under low humidity conditions, making it suitable for alkaline fuel cells. It can be applied to membranes and binders, water electrolysis devices, carbon dioxide reduction, or oxidation-reduction flow batteries.
Description
본 발명은 신규한 고내구성 가교 폴리(아릴 피페리디늄) 공중합체 이오노머, 음이온교환막 및 그 제조방법에 관한 것으로, 보다 상세하게는 고분자 골격 내 아릴 에테르 결합이 없으면서 반복단위 내 폴리스티렌 연결기에 의하여 가교된 피페리디늄 그룹이 도입된 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 합성하고, 이로부터 음이온교환막을 제조하여 알칼리 연료전지 및 수전해 장치 등에 응용하는 기술에 관한 것이다. The present invention relates to a new high -linal crosslinking poly (aryl piperidinium) copolymer ionomer, anion exchange film, and a method of manufacturing, more particularly, and is crosslinked by a repeated unit with no aryl ether bond in the polymer skeleton. This relates to a technology for synthesizing a cross-linked poly(aryl piperidinium) copolymer ionomer into which a piperidinium group is introduced, manufacturing an anion exchange membrane therefrom, and applying it to alkaline fuel cells and water electrolysis devices.
음이온교환막을 이용하는 알칼리막 연료전지(alkaline membrane fuel cell, AMFC) 및 수전해는 백금 대신에 니켈, 망간 등 저가의 비귀금속을 전극촉매로 사용할 수 있고, 우수한 성능과 더불어 가격 경쟁력 또한 월등히 높은 것으로 알려져 지속적인 연구가 이루어지고 있다. 그러나 운전 시 하이드록실라디칼 및 이온의 분해 거동으로 인한 낮은 장기안정성 문제 때문에 알칼리막 연료전지의 내구성을 향상시키기 위한 연구가 필요한 실정이다. Alkaline membrane fuel cells (AMFC) and water electrolysis using an anion exchange membrane can use inexpensive non-precious metals such as nickel and manganese as electrode catalysts instead of platinum, and are known to have excellent performance and significantly higher price competitiveness. Continuous research is being conducted. However, research is needed to improve the durability of alkaline membrane fuel cells due to low long-term stability problems due to the decomposition behavior of hydroxyl radicals and ions during operation.
또한, 통상의 알칼리성 고분자 전해질(alkaline polymer electrolyte, APE)은 고분자 골격과 양이온기로 구성되어 있는바, 각각 기계적 강도를 유지하고 OH-와 물 분자를 이동시킨다. 그러나 다수의 APE는 약한 고분자 골격(에테르 함유 구조)과 양이온기(예: 벤질트리메틸암모늄)로 인하여 제한된 알칼리 안정성(80℃ 1M NaOH에서 500h 이하), 불충분한 이온전도도 및 열악한 기계적 물성(인장강도<30 Mpa)을 가지므로 종래 음이온교환막 연료전지(anion exchange membrane fuel cell, AEMFC)는 낮은 출력밀도(<1 Wcm-2)와 셀 내구성을 갖는 문제점이 있다.In addition, a typical alkaline polymer electrolyte (APE) is composed of a polymer skeleton and a cationic group, and each maintains mechanical strength and moves OH - and water molecules. However, many APEs have limited alkali stability (less than 500 h in 1 M NaOH at 80°C), insufficient ionic conductivity, and poor mechanical properties (tensile strength < 500 h) due to their weak polymer skeleton (ether-containing structure) and cationic groups (e.g. benzyltrimethylammonium). 30 Mpa), the conventional anion exchange membrane fuel cell (AEMFC) has problems with low power density (<1 Wcm -2 ) and cell durability.
또한, 종래 APE는 이온전도도와 치수안정성 사이에 트레이드오프(trade-off) 관계를 가지고 있다. APE는 이온 수송을 촉진하기 위하여 충분한 전도성을 필요로 하는데, 높은 이온교환용량(ion exchange capacity, IEC)은 전도성을 향상시키는 가장 직접적인 방법인 반면, 높은 IEC는 높은 물 흡수율(water uptake, WU)과 팽윤비(swelling ratio, SW)를 유발하여 APE의 치수 안정성과 기계적 특성을 손상시키는 단점이 있다. 특히, 알칼리 에너지 장치의 장시간 작동을 위하여 기계적으로 질긴 막이 매우 중요한데, 종래 APE는 알칼리 안전성 시험 후 균열과 구멍과 같은 기계적 결함이 발생하여 안정성이 떨어지므로 알칼리 에너지 장치의 수명을 단축한다.Additionally, conventional APE has a trade-off relationship between ionic conductivity and dimensional stability. APE requires sufficient conductivity to promote ion transport, and while high ion exchange capacity (IEC) is the most direct way to improve conductivity, high IEC is associated with high water uptake (WU) and It has the disadvantage of damaging the dimensional stability and mechanical properties of APE by causing swelling ratio (SW). In particular, a mechanically strong membrane is very important for the long-term operation of alkaline energy devices, and conventional APE reduces stability due to mechanical defects such as cracks and holes after alkali safety tests, which shortens the lifespan of alkaline energy devices.
한편, 아직까지 고분자 골격 내 아릴 에테르 결합이 없으면서 반복단위 내 폴리스티렌 연결기에 의하여 가교된 피페리디늄 그룹이 도입된 폴리(아릴 피페리디늄) 이오노머가 합성된바 없으며, 이를 알칼리 연료전지용 막 및 바인더 또는 수전해 분야에 응용하는 기술에 대해서도 구체적으로 알려진 바 없다.Meanwhile, a poly(aryl piperidinium) ionomer in which a piperidinium group cross-linked by a polystyrene linker in the repeating unit is introduced without an aryl ether bond in the polymer backbone has not yet been synthesized, and it has been used as a membrane and binder for alkaline fuel cells. There is no specific information about the technology applied to the water electrolysis field.
그러므로 본 발명자 등은, 열적·화학적 안정성 및 기계적 물성이 우수한 방향족 고분자 이온교환막의 응용분야를 확대하기 위하여 연구를 거듭한 결과, 종래 APE가 갖는 낮은 화학적 안정성, 이온전도도, 기계적 물성, 치수안정성, 내구성 등과 같은 문제점을 고분자 골격 내 아릴 에테르 결합이 없고, 반복단위 내에 폴리스티렌 연결기에 의하여 가교된 피페리디늄 그룹을 포함함으로써 해결하고자 하였다.Therefore, the present inventors and others conducted repeated research to expand the application field of aromatic polymer ion exchange membranes with excellent thermal and chemical stability and mechanical properties. As a result, the low chemical stability, ionic conductivity, mechanical properties, dimensional stability, and durability of conventional APE were found. An attempt was made to solve problems such as the absence of an aryl ether bond in the polymer skeleton and the inclusion of a piperidinium group cross-linked by a polystyrene linkage in the repeating unit.
즉, 고분자 골격 내 아릴 에테르 결합이 없으면서 반복단위 내에 폴리스티렌 연결기에 의하여 가교된 피페리디늄 그룹이 도입된 폴리(아릴 피페리디늄) 공중합체 이오노머를 합성하며, 이로부터 음이온교환막을 제조함으로써 알칼리 연료전지용 막 및 바인더, 수전해 장치, 이산화탄소 환원, 또는 산화-환원 플로우 전지 등에 응용할 수 있음을 발견하여 본 발명을 완성하였다.In other words, a poly(aryl piperidinium) copolymer ionomer is synthesized without an aryl ether bond in the polymer skeleton and in which a piperidinium group cross-linked by a polystyrene linkage is introduced into the repeating unit, and an anion exchange membrane is manufactured from the poly(aryl piperidinium) ionomer for use in alkaline fuel cells. The present invention was completed by discovering that it can be applied to membranes and binders, water electrolysis devices, carbon dioxide reduction, or oxidation-reduction flow batteries.
본 발명은 상기와 같은 문제점을 감안하여 안출된 것으로, 본 발명의 제1 목적은 높은 화학적 안정성, 이온전도도, 기계적 물성, 치수안정성 및 내구성을 갖는 신규한 가교 폴리(아릴 피페리디늄) 공중합체 이오노머 및 그 제조방법을 제공하고자 하는 것이다.The present invention was developed in consideration of the above problems, and the first object of the present invention is to provide a novel cross-linked poly(aryl piperidinium) copolymer ionomer with high chemical stability, ionic conductivity, mechanical properties, dimensional stability, and durability. and its manufacturing method.
또한, 본 발명의 제2 목적은 상기 신규한 가교 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 음이온교환막을 제조함으로써 막의 과도한 팽윤을 억제하고, 기계적 물성, 알칼리 안정성 및 내구성이 크게 향상된 알칼리 연료전지용 막 및 바인더, 수전해 장치, 이산화탄소 환원, 또는 산화-환원 플로우 전지 등에 응용하고자 하는 것이다.In addition, the second object of the present invention is to produce an anion exchange membrane from the novel cross-linked poly(aryl piperidinium) copolymer ionomer, thereby suppressing excessive swelling of the membrane, and providing a membrane for an alkaline fuel cell with greatly improved mechanical properties, alkali stability, and durability. And it is intended to be applied to binders, water electrolysis devices, carbon dioxide reduction, or oxidation-reduction flow batteries.
상기한 바와 같은 목적을 달성하기 위한 본 발명은, 하기 <화학식 1>로 표시되는 반복단위를 갖는 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 제공한다.In order to achieve the above-described object, the present invention provides a crosslinked poly(aryl piperidinium) copolymer ionomer having a repeating unit represented by the following <Formula 1>.
<화학식 1><Formula 1>
(상기 화학식 1에서, Aryl은 하기 구조식으로 표시되는 화합물로부터 선택되는 상이한 2종의 것이고,(In Formula 1, Aryl is two different types selected from compounds represented by the following structural formulas,
,,,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수) , , , , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10)
m, n은 공중합체 이오노머의 반복단위 내 몰분율(%)로서 m>0, n>0, m+n=100이며, p는 20% 이하로 조절된 가교도를 의미한다)m, n are the mole fraction (%) within the repeating unit of the copolymer ionomer, where m>0, n>0, m+n=100, and p means the degree of crosslinking adjusted to 20% or less)
또한, 본 발명은 (I) 단량체로서 (a) 하기 구조식으로 표시되는 화합물로부터 선택되는 상이한 2종의 것, In addition, the present invention provides (I) as monomers (a) two different types selected from the compounds represented by the following structural formulas,
,,,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수) 및 (b) 1-메틸-4-피페리돈을 유기용매에 용해시켜 용액을 형성하는 단계; , , , , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10) and (b) dissolving 1-methyl-4-piperidone in an organic solvent to form a solution;
(II) 상기 용액에 강산 촉매를 서서히 부가, 교반 및 반응시켜 점성 용액을 얻는 단계; (III) 상기 점성 용액을 침전, 세척 및 건조하여 고체상의 중합체를 수득하는 단계; (IV) 상기 고체상의 중합체 및 강산 촉매를 유기용매에 용해시킨 중합체 용액에 K2CO3, 4-비닐벤질클로라이드 및 과량의 할로메탄을 부가 및 반응시켜 스티렌기가 도입된 4급 피페리디늄 염을 형성하는 단계; 및 (V) 중합체 용액을 침전, 세척 및 건조 후, 열처리 하는 단계;를 포함하는 가교 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조방법을 제공한다.(II) slowly adding a strong acid catalyst to the solution, stirring and reacting to obtain a viscous solution; (III) precipitating, washing and drying the viscous solution to obtain a solid polymer; (IV) K 2 CO 3 , 4-vinylbenzyl chloride and an excess amount of halomethane were added and reacted to the polymer solution in which the solid polymer and strong acid catalyst were dissolved in an organic solvent to produce a quaternary piperidinium salt into which a styrene group was introduced. forming step; and (V) precipitating, washing and drying the polymer solution, followed by heat treatment.
또한, 본 발명은 상기 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 포함하는 음이온교환막을 제공한다.Additionally, the present invention provides an anion exchange membrane comprising the cross-linked poly(aryl piperidinium) copolymer ionomer.
또한, 본 발명은 (i) 상기 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 유기용매에 용해시켜 고분자용액을 형성하는 단계; (ii) 상기 고분자용액을 유리판에 캐스팅 및 가열함으로써 유기용매를 제거하고 스티렌기 간의 가교반응이 동시에 유도된 막을 수득하는 단계; 및 (iii) 상기 수득한 막을 1M NaHCO3 또는 1M NaOH로 처리한 후, 초순수로 수회 세척 및 건조하는 단계;를 포함하는 음이온교환막의 제조방법을 제공한다.In addition, the present invention includes the steps of (i) dissolving the cross-linked poly(aryl piperidinium) copolymer ionomer in an organic solvent to form a polymer solution; (ii) casting and heating the polymer solution on a glass plate to obtain a film in which the organic solvent is removed and a cross-linking reaction between styrene groups is simultaneously induced; and (iii) treating the obtained membrane with 1M NaHCO 3 or 1M NaOH, followed by washing and drying several times with ultrapure water.
또한, 본 발명은 상기 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 포함하는 알칼리 연료전지용 바인더를 제공한다.Additionally, the present invention provides a binder for an alkaline fuel cell containing the cross-linked poly(aryl piperidinium) copolymer ionomer.
또한, 본 발명은 상기 음이온교환막을 포함하는 알칼리 연료전지를 제공한다.Additionally, the present invention provides an alkaline fuel cell including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 수전해 장치를 제공한다.Additionally, the present invention provides a water electrolysis device including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 이산화탄소 환원 장치를 제공한다.Additionally, the present invention provides a carbon dioxide reduction device including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 산화-환원 플로우 전지를 제공한다.Additionally, the present invention provides an oxidation-reduction flow battery including the anion exchange membrane.
본 발명에 따른 신규한 가교 폴리(아릴 피페리디늄) 공중합체 이오노머는 화학적 안정성, 이온전도도, 기계적 물성, 치수안정성 및 내구성이 매우 우수하다.The novel cross-linked poly(aryl piperidinium) copolymer ionomer according to the present invention has excellent chemical stability, ionic conductivity, mechanical properties, dimensional stability, and durability.
아울러 상기 가교 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 제조되는 음이온교환막은 기계적 내구성이 크게 향상될 뿐만 아니라, 막의 수분 보유 능력이 개선되어 저습도 조건에서도 연료전지의 작동이 가능하다.In addition, the anion exchange membrane manufactured from the cross-linked poly(aryl piperidinium) copolymer ionomer not only has greatly improved mechanical durability, but also has improved moisture retention ability of the membrane, enabling fuel cell operation even under low humidity conditions.
또한, 소수성 가교제를 사용함으로써 촉매층의 가스 투과성이 향상되고, 음극의 침수 문제가 완화되며, 특히 in-situ 가교방법으로 인하여 촉매층 내 이오노머의 접착력이 향상되고 연료전지 및 수전해 장치의 in-situ 내구성도 현저하게 향상된다.In addition, by using a hydrophobic cross-linking agent, the gas permeability of the catalyst layer is improved, the problem of flooding of the cathode is alleviated, and in particular, the in-situ cross-linking method improves the adhesion of the ionomer in the catalyst layer and improves the in-situ durability of fuel cells and water electrolysis devices. is also noticeably improved.
도 1은 본 발명의 실시예 7로부터 제조한 음이온교환막(OH- 형태)(실시예 1 내지 6에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 (a) 온도에 따른 팽창률(swelling ratio), (b) 시간에 따른 이온전도도(OH- conductivity)를 나타낸 그래프.
도 2는 본 발명의 실시예 7로부터 제조한 음이온교환막(I- 형태)(실시예 1 내지 6에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 이온채널크기 및 상분리도를 나타낸 원자현미경(AFM) 이미지.
도 3은 본 발명의 실시예 7로부터 제조한 음이온교환막(I- 형태)(실시예 1 내지 6에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 (a) 상온에서의 기계적 물성, (b) 동적기계열 특성을 나타낸 그래프.
도 4는 본 발명의 실시예 7로부터 제조한 음이온교환막(OH- 형태)(실시예 1 내지 6에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막을 80℃에서 2,160시간 동안 1M NaOH에 침지하기 전과 후의 Ex-situ 내구성 시험결과를 나타낸 그래프[(a) 30℃에서 OH-전도도 변화, (b) x-PFTP-PS-10의 1H NMR 스펙트럼, (c) 내구성 시험 후, OH-형태의 음이온교환막의 기계적 특성, (d) x-PFTP-PS-10의 열중량분석(TGA) 특성
도 5는 본 발명의 실시예 7로부터 제조한 음이온교환막(OH- 형태)(실시예 1 내지 6에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 낮은 상대습도 및 높은 온도에서의 연료전지 성능을 시험한 결과를 나타낸 그래프[시험조건: A/C PFTP 이오노머, 1,000/1,000 mL min-1 H2-O2 유량, 0.33 mg cm-2 A/C Pt/C, 90℃, 1.3/1.3 bar A/C 압력, (a) PFTP, (b) x-PFTP-PS-10, (c) x-PDTP-PS-20, (d) 상이한 상대습도를 갖는 연료전지의 peak power density(PPD) 요약]
도 6은 2.0 V에서 상이한 음이온교환막의 수전해 성능을 나타낸 그래프[시험조건: A/C PFBP-14 이오노머, 1M KOH feed, A/C IrO2/Pt/C, (a) 60℃에서 측정한 I-V 곡선, (b) 전기화학 임피던스 분광(EIS) 스펙트럼 및 (c) 80℃에서 측정한 I-V 곡선, (b) 전기화학 임피던스 분광(EIS) 스펙트럼].
Figure 1 shows some of the anion exchange membranes (OH - form) (made from the copolymer ionomers obtained in Examples 1 to 6) prepared in Example 7 of the present invention and some of the anion exchange membranes prepared in Comparative Examples 1 and 2 ( Graph showing a) swelling ratio according to temperature, (b) ionic conductivity (OH - conductivity) according to time.
Figure 2 shows some of the anion exchange membranes (I - form) prepared in Example 7 of the present invention (made from the copolymer ionomers obtained in Examples 1 to 6) and ions of the anion exchange membranes prepared in Comparative Examples 1 and 2. Atomic force microscopy (AFM) image showing channel size and phase separation.
Figure 3 shows some of the anion exchange membranes (I - form) prepared in Example 7 of the present invention (made from the copolymer ionomer obtained in Examples 1 to 6) and some of the anion exchange membranes prepared in Comparative Examples 1 and 2 ( Graph showing a) mechanical properties at room temperature, (b) dynamic mechanical properties.
Figure 4 shows some of the anion exchange membranes (OH - form) prepared in Example 7 of the present invention (made from the copolymer ionomer obtained in Examples 1 to 6) and the anion exchange membranes prepared in Comparative Examples 1 and 2. Graph showing the ex-situ durability test results before and after immersion in 1M NaOH for 2,160 hours at ℃ [(a) OH - conductivity change at 30℃, (b) 1 H NMR spectrum of x-PFTP-PS-10, ( c) Mechanical properties of the OH -type anion exchange membrane after durability test, (d) thermogravimetric analysis (TGA) properties of x-PFTP-PS-10
Figure 5 shows some of the anion exchange membranes (OH - form) prepared in Example 7 of the present invention (made from the copolymer ionomers obtained in Examples 1 to 6) and the low temperature of the anion exchange membranes prepared in Comparative Examples 1 and 2. Graph showing the results of testing fuel cell performance at relative humidity and high temperature [Test conditions: A/C PFTP ionomer, 1,000/1,000 mL min -1 H 2 -O 2 flow rate, 0.33 mg cm -2 A/C Pt /C, 90℃, 1.3/1.3 bar A/C pressure, (a) PFTP, (b) x-PFTP-PS-10, (c) x-PDTP-PS-20, (d) with different relative humidity. Summary of peak power density (PPD) of fuel cells]
Figure 6 is a graph showing the water electrolysis performance of different anion exchange membranes at 2.0 V [Test conditions: A/C PFBP-14 ionomer, 1M KOH feed, A/C IrO 2 /Pt/C, (a) measured at 60°C. IV curve, (b) electrochemical impedance spectroscopy (EIS) spectrum and (c) IV curve measured at 80°C, (b) electrochemical impedance spectroscopy (EIS) spectrum].
이하에서는 본 발명에 따른 신규한 고내구성 가교 폴리(아릴 피페리디늄) 공중합체 이오노머, 음이온교환막 및 그 제조방법에 관하여 상세히 설명하기로 한다.Hereinafter, the novel highly durable cross-linked poly(aryl piperidinium) copolymer ionomer, anion exchange membrane, and method for manufacturing the same according to the present invention will be described in detail.
본 발명에서는 하기 <화학식 1>로 표시되는 반복단위를 갖는 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 제공한다.The present invention provides a crosslinked poly(aryl piperidinium) copolymer ionomer having a repeating unit represented by the following <Chemical Formula 1>.
<화학식 1><Formula 1>
(상기 화학식 1에서, Aryl은 하기 구조식으로 표시되는 화합물로부터 선택되는 상이한 2종의 것이고,(In Formula 1, Aryl is two different types selected from compounds represented by the following structural formulas,
,,,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수) , , , , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10)
m, n은 공중합체 이오노머의 반복단위 내 몰분율(%)로서 m>0, n>0, m+n=100이며, p는 20% 이하로 조절된 가교도를 의미한다)m, n are the mole fraction (%) within the repeating unit of the copolymer ionomer, where m>0, n>0, m+n=100, and p means the degree of crosslinking adjusted to 20% or less)
상기 화학식 1에서 보는 바와 같이, 본 발명에 따른 가교 폴리(아릴 피페리디늄) 공중합체 이오노머는 기본적으로 고분자 골격 내에 아릴 에테르기를 포함하지 않고, 폴리스티렌 연결기에 의하여 가교된 피페리디늄 그룹을 포함함으로써 제막 성능과 화학적 안정성이 우수하다.As shown in Chemical Formula 1, the cross-linked poly(aryl piperidinium) copolymer ionomer according to the present invention does not basically contain an aryl ether group in the polymer skeleton, but is formed by including a piperidinium group cross-linked by a polystyrene linking group. Excellent performance and chemical stability.
또한, 이온전도도, 기계적 물성, 치수안정성 및 내구성도 크게 향상된다. 특히, 가교구조를 형성하기 위하여 소수성 가교제인 비닐벤질클로라이드를 사용함으로써 APE의 알칼리 안정성을 향상시키고, 팽윤과 이온전도도 사이의 균형을 맞춘다. Additionally, ionic conductivity, mechanical properties, dimensional stability, and durability are greatly improved. In particular, the use of vinylbenzyl chloride, a hydrophobic cross-linking agent, to form a cross-linking structure improves the alkali stability of APE and balances swelling and ionic conductivity.
아울러 알칼리 연료전지 촉매층의 가스 투과성이 향상되고, 음극의 침수 문제가 완화되며, 특히 in-situ 가교방법으로 인하여 촉매층 내 이오노머의 접착력이 향상되고 연료전지 및 수전해 장치의 in-situ 내구성도 현저하게 향상된다.In addition, the gas permeability of the alkaline fuel cell catalyst layer is improved, the problem of flooding of the cathode is alleviated, and in particular, the adhesion of the ionomer in the catalyst layer is improved due to the in-situ crosslinking method, and the in-situ durability of the fuel cell and water electrolysis device is significantly improved. It improves.
또한, 본 발명은 (I) 단량체로서 (a) 하기 구조식으로 표시되는 화합물로부터 선택되는 상이한 2종의 것, In addition, the present invention provides (I) as monomers (a) two different types selected from the compounds represented by the following structural formulas,
,,,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수) 및 (b) 1-메틸-4-피페리돈을 유기용매에 용해시켜 용액을 형성하는 단계; , , , , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10) and (b) dissolving 1-methyl-4-piperidone in an organic solvent to form a solution;
(II) 상기 용액에 강산 촉매를 서서히 부가, 교반 및 반응시켜 점성 용액을 얻는 단계; (III) 상기 점성 용액을 침전, 세척 및 건조하여 고체상의 중합체를 수득하는 단계; (IV) 상기 고체상의 중합체 및 강산 촉매를 유기용매에 용해시킨 중합체 용액에 K2CO3, 4-비닐벤질클로라이드 및 과량의 할로메탄을 부가 및 반응시켜 스티렌기가 도입된 4급 피페리디늄 염을 형성하는 단계; 및 (V) 중합체 용액을 침전, 세척 및 건조 후, 열처리 하는 단계;를 포함하는 가교 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조방법을 제공한다.(II) slowly adding a strong acid catalyst to the solution, stirring and reacting to obtain a viscous solution; (III) precipitating, washing and drying the viscous solution to obtain a solid polymer; (IV) K 2 CO 3 , 4-vinylbenzyl chloride and an excess amount of halomethane were added and reacted to the polymer solution in which the solid polymer and strong acid catalyst were dissolved in an organic solvent to produce a quaternary piperidinium salt into which a styrene group was introduced. forming step; and (V) precipitating, washing and drying the polymer solution, followed by heat treatment.
이때, 상기 (I) 단계의 유기용매는 할로겐계 용매로서 디클로로메탄, 클로로포름, 디클로로에탄, 디브로모메탄 및 테트라클로로에탄으로 이루어진 군으로부터 선택된 1종 이상의 것일 수 있고, 디클로로메탄을 바람직하게 사용한다.At this time, the organic solvent in step (I) may be one or more halogen-based solvents selected from the group consisting of dichloromethane, chloroform, dichloroethane, dibromomethane, and tetrachloroethane, and dichloromethane is preferably used. .
또한, 상기 (II) 또는 (IV) 단계의 강산 촉매는 트리플루오로아세트산, 트리플루오로메탄술폰산, 펜타플루오로에탄술폰산, 헵타플루오로-1-프로판술폰산, 퍼플루오로프로피온산, 헵타플루오로부티르산, 또는 이들의 혼합물일 수 있다.In addition, the strong acid catalyst in step (II) or (IV) is trifluoroacetic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, perfluoropropionic acid, and heptafluorobutyric acid. , or a mixture thereof.
또한, 상기 (IV) 단계의 유기용매는 N-메틸피롤리돈, 디메틸아세트아미드, 디메틸술폭시드 또는 디메틸포름아미드일 수 있다.Additionally, the organic solvent in step (IV) may be N-methylpyrrolidone, dimethylacetamide, dimethyl sulfoxide, or dimethylformamide.
또한, 상기 (IV) 단계에서는 4급 피페리디늄 염을 형성하기 위하여 중합체를 할로메탄과 반응시키는바, 상기 할로메탄은 플루오로메탄, 클로로메탄, 브로모메탄 또는 아이오도메탄일 수 있고, 아이오도메탄을 바람직하게 사용한다.In addition, in step (IV), the polymer is reacted with halomethane to form a quaternary piperidinium salt, and the halomethane may be fluoromethane, chloromethane, bromomethane, or iodomethane, and io Domethane is preferably used.
또한, 본 발명은 상기 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 포함하는 음이온교환막을 제공한다.Additionally, the present invention provides an anion exchange membrane comprising the cross-linked poly(aryl piperidinium) copolymer ionomer.
본 발명에 따른 상기 음이온교환막은 기계적 내구성이 크게 향상될 뿐만 아니라, 제한된 팽윤비를 나타내고 이온전도도 및 치수안정성이 잘 제어되며, 또한 막의 수분 보유 능력이 개선되어 저습도 조건에서도 연료전지의 작동이 가능하다.The anion exchange membrane according to the present invention not only has significantly improved mechanical durability, but also exhibits a limited swelling ratio and well-controlled ion conductivity and dimensional stability. Additionally, the moisture retention capacity of the membrane is improved, enabling fuel cell operation even under low humidity conditions. do.
또한, 본 발명은 (i) 상기 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 유기용매에 용해시켜 고분자용액을 형성하는 단계; (ii) 상기 고분자용액을 유리판에 캐스팅 및 가열함으로써 유기용매를 제거하고 스티렌기 간의 가교반응이 동시에 유도된 막을 수득하는 단계; 및 (iii) 상기 수득한 막을 1M NaHCO3 또는 1M NaOH로 처리한 후, 초순수로 수회 세척 및 건조하는 단계;를 포함하는 음이온교환막의 제조방법을 제공한다.In addition, the present invention includes the steps of (i) dissolving the cross-linked poly(aryl piperidinium) copolymer ionomer in an organic solvent to form a polymer solution; (ii) casting and heating the polymer solution on a glass plate to obtain a film in which the organic solvent is removed and a cross-linking reaction between styrene groups is simultaneously induced; and (iii) treating the obtained membrane with 1M NaHCO 3 or 1M NaOH, followed by washing and drying several times with ultrapure water.
이때, 상기 (i) 단계의 유기용매는 N-메틸피롤리돈, 디메틸아세트아미드, 디메틸술폭시드 또는 디메틸포름아미드일 수 있다.At this time, the organic solvent in step (i) may be N-methylpyrrolidone, dimethylacetamide, dimethyl sulfoxide, or dimethylformamide.
또한, 상기 고분자용액의 농도는 2~30 중량%인 것이 바람직하고, 그 농도가 3.0~5.0 중량%인 것이 더욱 바람직하다. 고분자용액의 농도가 2 중량% 미만이면 막의 형성능이 떨어질 수 있고, 30 중량%를 초과하면 점도가 너무 높아져 제막 후 막이 물성이 저하될 수 있다.In addition, the concentration of the polymer solution is preferably 2 to 30% by weight, and more preferably 3.0 to 5.0% by weight. If the concentration of the polymer solution is less than 2% by weight, the film forming ability may be reduced, and if it exceeds 30% by weight, the viscosity may become too high and the physical properties of the film may be deteriorated after film formation.
또한, 상기 (ii) 단계에서는 80~90℃ 오븐에서 24시간 동안 유기용매를 서서히 제거한 후, 120~150℃ 진공오븐에서 12시간 동안 더 가열함으로써 유기용매를 완전히 제거함과 동시에 스티렌기 간의 가교반응이 유도된다. In addition, in step (ii), the organic solvent is gradually removed in an oven at 80-90°C for 24 hours, and then heated in a vacuum oven at 120-150°C for 12 hours to completely remove the organic solvent and at the same time cause a crosslinking reaction between styrene groups. It is induced.
본 발명에 따른 가교 폴리(아릴 피페리디늄) 공중합체 이오노머의 합성과정은 아래 scheme 1의 반응경로로 나타낼 수 있다.The synthesis process of the cross-linked poly(aryl piperidinium) copolymer ionomer according to the present invention can be represented by the reaction route in Scheme 1 below.
Scheme 1. 가교 폴리(아릴 피페리디늄) 공중합체 이오노머의 합성 경로(상기 반응식에서, Aryl, m, n, p는 상기 화학식 1에서 정의한 바와 같다) Scheme 1. Synthesis route of cross-linked poly(aryl piperidinium) copolymer ionomer (In the above reaction scheme, Aryl, m, n, p are as defined in Formula 1 above)
또한, 본 발명은 상기 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 포함하는 알칼리 연료전지용 바인더를 제공한다.Additionally, the present invention provides a binder for an alkaline fuel cell containing the cross-linked poly(aryl piperidinium) copolymer ionomer.
또한, 본 발명은 상기 음이온교환막을 포함하는 알칼리 연료전지를 제공한다.Additionally, the present invention provides an alkaline fuel cell including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 수전해 장치를 제공한다.Additionally, the present invention provides a water electrolysis device including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 이산화탄소 환원 장치를 제공한다.Additionally, the present invention provides a carbon dioxide reduction device including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 산화-환원 플로우 전지를 제공한다.Additionally, the present invention provides an oxidation-reduction flow battery including the anion exchange membrane.
이하 본 발명에 따른 실시예 및 비교예를 첨부된 도면과 함께 구체적으로 설명한다.Hereinafter, examples and comparative examples according to the present invention will be described in detail with the accompanying drawings.
[실시예 1 내지 2] 가교 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조[Examples 1 to 2] Preparation of crosslinked poly(aryl piperidinium) copolymer ionomer
단량체로서 디페닐에탄(1.0252 g, 5.625 mmol), 터페닐(3.885 g, 16.857 mmol), 및 1-메틸-4-피페리돈(2.8005 g, 24.750 mmol)을 100mL 반응기에 투입한 후, 디클로로메탄(DCM, 18 mL)을 부가하여 교반하면서 단량체들을 용해시켜 용액을 형성하였다. 상기 용액의 온도를 1℃로 냉각시킨 후, 트리플루오로아세트산(TFA, 2.7 mL) 및 트리플루오로메탄술폰산(TFSA, 18 mL)의 혼합물을 상기 용액에 서서히 부가, 교반 및 12시간 반응시켜 점성 용액을 얻었다. 상기 점성 용액을 500 mL의 증류수에 부어 침전, 탈이온수로 수회 세척 및 70℃ 오븐에서 24시간 건조하여 고체상의 폴리(디페닐-co-터페닐 N-메틸 피페리딘) 중합체를 제조하였다.Diphenylethane (1.0252 g, 5.625 mmol), terphenyl (3.885 g, 16.857 mmol), and 1-methyl-4-piperidone (2.8005 g, 24.750 mmol) as monomers were added to a 100 mL reactor, then dichloromethane ( DCM, 18 mL) was added and stirred to dissolve the monomers to form a solution. After cooling the temperature of the solution to 1°C, a mixture of trifluoroacetic acid (TFA, 2.7 mL) and trifluoromethanesulfonic acid (TFSA, 18 mL) was slowly added to the solution, stirred, and reacted for 12 hours to increase viscosity. A solution was obtained. The viscous solution was poured into 500 mL of distilled water to precipitate, washed several times with deionized water, and dried in an oven at 70°C for 24 hours to prepare solid poly(diphenyl-co-terphenyl N-methyl piperidine) polymer.
다음으로, 상기 제조한 중합체(4 g, 8.63 mmol) 및 트리플루오로아세트산(TFA, 0.64 mL)을 디메틸술폭시드(80 mL)에 용해시켜 중합체 용액을 얻은 후, 상기 중합체 용액에 K2CO3(2.98 g, 21.57 mmol) 및 4-비닐벤질클로라이드(0.1317 g, 0.863 mmol)를 넣고 상온에서 24시간 연속 교반한다. 그 후, 상기 중합체 용액에 아이오도메탄(CH3I, 4.4 g, 31 mmol)을 부가 및 상온, 암실에서 24시간 반응시켜 4급 피페리디늄 염을 형성하였다. 다음으로, 중합체 용액을 에틸아세테이트 800mL에 침전, 여과, 탈이온수로 수회 세척 및 50℃ 진공오븐에서 24시간 건조하여 고체상의 가교 폴리(아릴 피페리디늄) 공중합체 이오노머(가교도 10%)를 제조하였고, 이를 x-PDTP-PS-10이라 명명하였다(실시예 1).Next, the prepared polymer (4 g, 8.63 mmol) and trifluoroacetic acid (TFA, 0.64 mL) were dissolved in dimethyl sulfoxide (80 mL) to obtain a polymer solution, and then K 2 CO 3 was added to the polymer solution. (2.98 g, 21.57 mmol) and 4-vinylbenzyl chloride (0.1317 g, 0.863 mmol) were added and stirred continuously for 24 hours at room temperature. Afterwards, iodomethane (CH 3 I, 4.4 g, 31 mmol) was added to the polymer solution and reacted at room temperature in the dark for 24 hours to form a quaternary piperidinium salt. Next, the polymer solution was precipitated in 800 mL of ethyl acetate, filtered, washed several times with deionized water, and dried in a vacuum oven at 50°C for 24 hours to prepare a solid cross-linked poly(aryl piperidinium) copolymer ionomer (crosslinking degree 10%). and was named x-PDTP-PS-10 (Example 1).
또한, 실시예 1과 동일한 방법으로 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 제조하되, 가교도를 20%로 조절하였으며, 이를 x-PDTP-PS-20이라 명명하였다(실시예 2).In addition, a cross-linked poly(aryl piperidinium) copolymer ionomer was prepared in the same manner as in Example 1, but the degree of cross-linking was adjusted to 20%, and it was named x-PDTP-PS-20 (Example 2).
[실시예 3 내지 4] 가교 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조[Examples 3 to 4] Preparation of crosslinked poly(aryl piperidinium) copolymer ionomer
단량체로서 실시예 1, 2의 디페닐에탄 대신에 9,9'-디메틸플루오렌을 사용한 것을 제외하고는 실시예 1, 2와 동일한 방법으로 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 제조하였고, 이를 각각 x-PFTP-PS-10(가교도 10%, 실시예 3) 및 x-PFTP-PS-20(가교도 20%, 실시예 4)이라 명명하였다.Cross-linked poly(aryl piperidinium) copolymer ionomer was prepared in the same manner as Examples 1 and 2, except that 9,9'-dimethylfluorene was used as a monomer instead of diphenylethane in Examples 1 and 2. , which were named x-PFTP-PS-10 (crosslinking degree 10%, Example 3) and x-PFTP-PS-20 (crosslinking degree 20%, Example 4), respectively.
[실시예 5 내지 6] 가교 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조[Examples 5 to 6] Preparation of crosslinked poly(aryl piperidinium) copolymer ionomer
단량체로서 실시예 3, 4의 터페닐 대신에 바이페닐을 사용한 것을 제외하고는 실시예 3, 4와 동일한 방법으로 가교 폴리(아릴 피페리디늄) 공중합체 이오노머를 제조하였고, 이를 각각 x-PFBP-PS-10(가교도 10%, 실시예 5) 및 x-PFBP-PS-20(가교도 20%, 실시예 6)이라 명명하였다.Cross-linked poly(aryl piperidinium) copolymer ionomers were prepared in the same manner as in Examples 3 and 4, except that biphenyl was used instead of terphenyl in Examples 3 and 4 as the monomer, and x-PFBP- They were named PS-10 (crosslinking degree 10%, Example 5) and x-PFBP-PS-20 (crosslinking degree 20%, Example 6).
상기 실시예 1 내지 6으로부터 제조한 가교 폴리(아릴 피페리디늄) 공중합체 이오노머의 핵자기공명(1H NMR) 분석 결과, 4-비닐벤질클로라이드 내 비닐 그룹(-CH2=CH-)의 chemical shift(5.3 ppm, 5.8 ppm, 6.75 ppm)를 확인함으로써 가교구조가 형성되었음을 알 수 있었다. As a result of nuclear magnetic resonance ( 1H NMR) analysis of the cross-linked poly(aryl piperidinium) copolymer ionomer prepared from Examples 1 to 6, the chemical structure of the vinyl group (-CH 2 =CH-) in 4-vinylbenzyl chloride was determined. It was confirmed that a cross-linked structure was formed by confirming the shift (5.3 ppm, 5.8 ppm, 6.75 ppm).
[실시예 7] 가교 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 음이온교환막의 제조[Example 7] Preparation of anion exchange membrane from cross-linked poly(aryl piperidinium) copolymer ionomer
상기 실시예 1 내지 6으로부터 제조한 가교 폴리(아릴 피페리디늄) 공중합체 이오노머(1.0 g)를 디메틸술폭시드(25 mL)에 용해시켜 고분자용액을 형성하였다. 이어서, 상기 고분자용액을 0.45 ㎛ PTFE 필터로 여과하고, 투명한 용액을 21 x 24 cm 유리판에 캐스팅하였다. 상기 캐스팅 용액을 90℃ 오븐에서 24시간 가열하고, 140℃ 진공오븐에서 12시간 더 가열하여 용매를 완전히 제거함과 아울러 막 가열 과정에서 스티렌기 간의 가교반응이 동시에 유도된 옅은 노란색의 투명한 막을 얻었다.The cross-linked poly(aryl piperidinium) copolymer ionomer (1.0 g) prepared in Examples 1 to 6 was dissolved in dimethyl sulfoxide (25 mL) to form a polymer solution. Subsequently, the polymer solution was filtered through a 0.45 ㎛ PTFE filter, and the transparent solution was cast on a 21 x 24 cm glass plate. The casting solution was heated in an oven at 90°C for 24 hours and further heated in a vacuum oven at 140°C for 12 hours to completely remove the solvent, and a light yellow transparent film was obtained in which a crosslinking reaction between styrene groups was simultaneously induced during the film heating process.
상기 수득한 I- 형태의 막을 1M NaOH 수용액에 24시간 침지하여 카운터 이온을 OH-로 전환시키고 초순수로 수회 세척 및 건조함으로써 음이온교환막을 제조하였다(얻어진 음이온교환막 샘플의 명명은 실시예 1 내지 6으로부터 제조한 가교 폴리(아릴 피페리디늄) 공중합체 이오노머에서 명명한 것과 같다).The obtained I - form membrane was immersed in 1M NaOH aqueous solution for 24 hours to convert the counter ion into OH - and washed with ultrapure water several times and dried to prepare an anion exchange membrane (the names of the obtained anion exchange membrane samples are from Examples 1 to 6. Same as the name given to the cross-linked poly(aryl piperidinium) copolymer ionomer prepared).
[비교예 1] 가교구조를 갖지 않는 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 음이온교환막의 제조[Comparative Example 1] Preparation of anion exchange membrane from poly(aryl piperidinium) copolymer ionomer without crosslinking structure
실시예 1의 4-비닐벤질클로라이드를 부가하여 가교반응 시키는 과정을 수행하지 않는 것을 제외하고는 실시예 1과 동일한 방법으로 얻어진 폴리(디페닐-co-터페닐 N, N-디메틸피페리디늄) 공중합체 이오노머를 실시예 7과 동일한 방법으로 제막함으로써 가교구조를 갖지 않는 음이온교환막을 제조하였으며, 이를 PDTP(또는 PDTP-25: 반복단위 내 디페닐 블록의 몰분율이 25%)라고 명명하였다.Poly(diphenyl-co-terphenyl N, N-dimethylpiperidinium) obtained in the same manner as in Example 1, except that the crosslinking reaction process by adding 4-vinylbenzyl chloride in Example 1 was not performed. An anion exchange membrane without a cross-linked structure was prepared by forming a copolymer ionomer film in the same manner as in Example 7, and it was named PDTP (or PDTP-25: mole fraction of diphenyl block in the repeating unit is 25%).
[비교예 2] 가교구조를 갖지 않는 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 음이온교환막의 제조[Comparative Example 2] Preparation of anion exchange membrane from poly(aryl piperidinium) copolymer ionomer without crosslinking structure
실시예 3의 4-비닐벤질클로라이드를 부가하여 가교반응 시키는 과정을 수행하지 않는 것을 제외하고는 실시예 3과 동일한 방법으로 얻어진 폴리(플루오렌-co-터페닐 N, N-디메틸피페리디늄) 공중합체 이오노머를 실시예 7과 동일한 방법으로 제막함으로써 가교구조를 갖지 않는 음이온교환막을 제조하였으며, 이를 PFTP(또는 PFTP-8: 반복단위 내 플루오레닐 블록의 몰분율이 8%)라고 명명하였다.Poly(fluorene-co-terphenyl N, N-dimethylpiperidinium) obtained in the same manner as Example 3, except that the crosslinking reaction process by adding 4-vinylbenzyl chloride in Example 3 was not performed. An anion exchange membrane without a cross-linked structure was prepared by forming a copolymer ionomer film in the same manner as in Example 7, and it was named PFTP (or PFTP-8: mole fraction of fluorenyl block in the repeating unit is 8%).
[시험예] [Test example]
본 발명의 실시예 및 비교예로부터 제조한 음이온교환막의 기계적 물성, 이온교환능(IEC), 함수율(WU), 팽창률(SR), 수분보유율(λ), 이온전도도 및 연료전지 성능 등의 시험 데이터는 본 발명의 발명자 등에 의한 선출원 공개특허 제10-2021-0071810호에 기재된 방법에 의하여 측정 및 평가하였다.Test data such as mechanical properties, ion exchange capacity (IEC), water content (WU), expansion rate (SR), water retention rate (λ), ion conductivity, and fuel cell performance of the anion exchange membrane prepared from the examples and comparative examples of the present invention are It was measured and evaluated by the method described in the previously filed patent publication No. 10-2021-0071810 by the inventor of the present invention.
먼저, 하기 표 1에는 본 발명의 실시예 7로부터 제조한 음이온교환막(실시예 1 내지 4에서 얻은 공중합체 이오노머로부터 제조한 것) 및 비교예 1, 2로부터 제조한 음이온교환막 샘플의 이온교환능(IEC), 함수율(WU), 팽창률(SR), 수분보유율(λ) 및 이온전도도(σ)를 나타내었다.First, Table 1 below shows the ion exchange capacity (IEC) of the anion exchange membrane samples prepared in Example 7 of the present invention (made from the copolymer ionomer obtained in Examples 1 to 4) and the anion exchange membrane samples prepared in Comparative Examples 1 and 2. ), water content (WU), swelling ratio (SR), water retention rate (λ), and ionic conductivity (σ).
(mmolg-1)IEC a
(mmolg -1 )
(mS cm-1)σ(OH - ) b
(mS cm -1 )
a: OH- form; b:at 30℃a: OH - form; b:at 30℃
또한, 도 1에는 본 발명의 실시예 7로부터 제조한 음이온교환막(OH- 형태)(실시예 1 내지 6에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 (a) 온도에 따른 팽창률(swelling ratio), (b) 시간에 따른 이온전도도(OH- conductivity)를 나타내었다.In addition, Figure 1 shows some of the anion exchange membranes (OH - form) prepared in Example 7 of the present invention (made from the copolymer ionomer obtained in Examples 1 to 6) and anion exchange membranes prepared in Comparative Examples 1 and 2. (a) swelling ratio according to temperature, (b) ionic conductivity (OH - conductivity) according to time.
상기 표 1 및 도 1에서 보는 바와 같이, 가교구조를 갖는 음이온교환막은 치수안정성이 더 우수함을 알 수 있는데, 낮은 팽창률(50%)의 음이온교환막은 고성능의 연료전지를 위하여 매우 중요한 요소이다.As shown in Table 1 and Figure 1, it can be seen that the anion exchange membrane with a cross-linked structure has better dimensional stability, and an anion exchange membrane with a low expansion rate (50%) is a very important element for a high-performance fuel cell.
게다가 가교구조를 갖는 음이온교환막은 낮은 이온교환능과 소수성 가교제로 인하여 가교구조를 갖지 않는 음이온교환막보다 다소 낮은 이온전도도를 보였다. 특히, x-PFTP-PS-10 음이온교환막은 90℃에서 150 mS cm-1 이상의 높은 OH- 전도도를 가지며, 이는 대부분의 음이온교환막보다 우수한 것으로 평가되었다.In addition, the anion exchange membrane with a cross-linked structure showed slightly lower ionic conductivity than the anion exchange membrane without a cross-linked structure due to its low ion exchange capacity and hydrophobic cross-linking agent. In particular, the x-PFTP-PS-10 anion exchange membrane has a high OH - conductivity of more than 150 mS cm -1 at 90°C, which was evaluated to be superior to most anion exchange membranes.
또한, 도 2에는 본 발명의 실시예 7로부터 제조한 음이온교환막(I- 형태)(실시예 1 내지 6에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 이온채널크기 및 상분리도를 나타낸 원자현미경(AFM) 이미지를 도시하였다.In addition, Figure 2 shows some of the anion exchange membranes (I - form) prepared in Example 7 of the present invention (made from the copolymer ionomer obtained in Examples 1 to 6) and anion exchange membranes prepared in Comparative Examples 1 and 2. An atomic force microscope (AFM) image showing the ion channel size and phase separation is shown.
도 2에서 어두운 부분은 암모늄기와 결합수에 의해 응집된 친수성 상을 나타내고, 노란색 부부은 강성 고분자에 의해 형성된 소수성 상을 나타낸다. 모든 음이온교환막이 유사한 특징을 가진 명확한 친수성/소수성 상분리 형태를 보이는 반면, 친수성 상 영역(이온채널)의 폭과 면적 비율은 다르다. 가교구조를 갖지 않는 음이온교환막과 비교하여 가교구조를 갖는 음이온교환막은 소수성 가교제로 인하여 더 좁지만 연속적인 이온채널을 나타내었다.In Figure 2, the dark portion represents the hydrophilic phase aggregated by ammonium groups and bound water, and the yellow portion represents the hydrophobic phase formed by the rigid polymer. While all anion exchange membranes show a clear hydrophilic/hydrophobic phase separation pattern with similar characteristics, the width and area ratio of the hydrophilic phase region (ion channel) are different. Compared to the anion exchange membrane without a cross-linking structure, the anion exchange membrane with a cross-linking structure showed narrower but continuous ion channels due to the hydrophobic cross-linking agent.
또한, 도 3에는 본 발명의 실시예 7로부터 제조한 음이온교환막(I- 형태)(실시예 1 내지 6에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 (a) 상온에서의 기계적 물성, (b) 동적기계열 특성을 나타내었다.In addition, Figure 3 shows some of the anion exchange membranes (I - form) prepared in Example 7 of the present invention (made from the copolymer ionomer obtained in Examples 1 to 6) and anion exchange membranes prepared in Comparative Examples 1 and 2. (a) Mechanical properties at room temperature and (b) dynamic mechanical properties are shown.
모든 음이온교환막이 종래 알려진 음이온교환막보다 우수한 기계적 특성을 보였고, 가교구조를 갖는 음이온교환막은 가교구조를 갖지 않는 음이온교환막과 비교하여 80Mpa 이상의 높은 인장강도를 가지며, 특히 가교도가 10%인 x-PDTP-PS-10 및 x-PFTP-PS-10 음이온교환막은 적절한 연신율(25%)과 함께 70Mpa 이상의 높은 인장강도를 나타내었다.All anion exchange membranes showed superior mechanical properties to conventionally known anion exchange membranes, and the anion exchange membrane with a cross-linked structure had a higher tensile strength of more than 80Mpa compared to the anion exchange membrane without a cross-linked structure, especially x-PDTP- with a cross-linking degree of 10%. PS-10 and x-PFTP-PS-10 anion exchange membranes showed high tensile strength of over 70Mpa with appropriate elongation (25%).
아울러 가교구조를 갖는 음이온교환막은 높은 저장 모듈러스를 보였으며(PFTP 시리즈: >2000Mpa), 380℃ 이상의 높은 유리전이온도(Tg)를 나타내었다.In addition, the anion exchange membrane with a cross-linked structure showed a high storage modulus (PFTP series: >2000Mpa) and a high glass transition temperature (T g ) of over 380°C.
또한, 도 4에는 본 발명의 실시예 7로부터 제조한 음이온교환막(OH- 형태)(실시예 1 내지 6에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막을 80℃에서 2,160시간 동안 1M NaOH에 침지하기 전과 후의 Ex-situ 내구성 시험결과를 나타낸 그래프[(a) 30℃에서 OH-전도도 변화, (b) x-PFTP-PS-10의 1H NMR 스펙트럼, (c) 내구성 시험 후, OH-형태의 음이온교환막의 기계적 특성, (d) x-PFTP-PS-10의 열중량분석(TGA) 특성을 나타내었다.In addition, Figure 4 shows some of the anion exchange membranes (OH - form) prepared in Example 7 of the present invention (made from the copolymer ionomers obtained in Examples 1 to 6) and anion exchange membranes prepared in Comparative Examples 1 and 2. Graph showing ex-situ durability test results before and after immersing the membrane in 1M NaOH for 2,160 hours at 80℃ [(a) OH - conductivity change at 30℃, (b) 1 H NMR spectrum of x-PFTP-PS-10 , (c) mechanical properties of the OH - type anion exchange membrane after the durability test, and (d) thermogravimetric analysis (TGA) properties of x-PFTP-PS-10.
가교구조를 갖는 음이온교환막은 가교구조를 갖지 않는 음이온교환막과 비슷한 알칼리 안정성을 보였는데, 2,160시간 동안 알칼리 처리 후 약간의 이온전도도 손실(<10%)만 측정되었다.The anion exchange membrane with a cross-linked structure showed similar alkali stability to the anion exchange membrane without a cross-linked structure, but only a slight loss of ionic conductivity (<10%) was measured after alkali treatment for 2,160 hours.
PFTP 시리즈는 2,160시간 동안 알칼리 안정성 시험 후, 90% 이상의 우수한 기계적 특성(인장강도>50Mpa, 연신율>30%)을 유지하였는바. 이는 연료전지에 적용하기에 충분한 기계적 강도로 평가되었다.The PFTP series maintained more than 90% of its excellent mechanical properties (tensile strength > 50Mpa, elongation > 30%) after an alkali stability test for 2,160 hours. This was evaluated as sufficient mechanical strength for application to fuel cells.
한편, 알칼리 처리 전과 후에 가교구조를 갖는 음이온교환막의 열중량분석(TGA)을 통하여도 1M NaOH에 2,160시간 동안 침지 후에 여전히 고분자 골격 내에 암모늄기를 유지함을 알 수 있었다.Meanwhile, through thermogravimetric analysis (TGA) of an anion exchange membrane with a cross-linked structure before and after alkali treatment, it was found that ammonium groups were still maintained in the polymer skeleton after immersion in 1 M NaOH for 2,160 hours.
또한, 도 5에는 본 발명의 실시예 7로부터 제조한 음이온교환막(OH- 형태)(실시예 1 내지 6에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 낮은 상대습도 및 높은 온도에서의 연료전지 성능을 시험한 결과[시험조건: A/C PFTP 이오노머, 1,000/1,000 mL min-1 H2-O2 유량, 0.33 mg cm-2 A/C Pt/C, 90℃, 1.3/1.3 bar A/C 압력, (a) PFTP, (b) x-PFTP-PS-10, (c) x-PDTP-PS-20, (d) 상이한 상대습도를 갖는 연료전지의 peak power density(PPD) 요약]를 나타내었다.In addition, Figure 5 shows some of the anion exchange membranes (OH - form) prepared in Example 7 of the present invention (made from the copolymer ionomer obtained in Examples 1 to 6) and anion exchange membranes prepared in Comparative Examples 1 and 2. Results of testing fuel cell performance at low relative humidity and high temperature [Test conditions: A/C PFTP ionomer, 1,000/1,000 mL min -1 H 2 -O 2 flow rate, 0.33 mg cm -2 A/C Pt/ C, 90°C, 1.3/1.3 bar A/C pressure, (a) PFTP, (b) x-PFTP-PS-10, (c) x-PDTP-PS-20, (d) fuels with different relative humidity. Summary of peak power density (PPD) of the battery] is shown.
도 5에서 보는 바와 같이, 가교구조를 갖는 음이온교환막 연료전지는 극도로 낮은 상대습도에서 안정적인 PPD를 나타내었다. 특히, x-PDTP-PS-10 및 x-PFTP-PS-10 음이온교환막 기반의 연료전지 셀은 각각 30/30% 상대습도 및 0/30% 상대습도에서 ~1Wcm-2 및 ~0.85Wcm-2의 PPD를 얻을 수 있었다.As shown in Figure 5, the anion exchange membrane fuel cell with a cross-linked structure showed stable PPD at extremely low relative humidity. In particular, x-PDTP-PS-10 and x-PFTP-PS-10 anion exchange membrane-based fuel cells have ~1Wcm -2 and ~0.85Wcm -2 at 30/30% relative humidity and 0/30% relative humidity, respectively. was able to obtain a PPD of
게다가 가교구조를 갖는 음이온교환막 기반의 연료전지 셀은 높은 상대습도와 낮은 상대습도 조건일 때 낮은 PPD 차이를 나타내므로 가교구조를 갖는 음이온교환막은 네트워크 구조로 인하여 종래 가교구조를 갖지 않는 음이온교환막보다 더 높은 함수율을 갖는다.In addition, a fuel cell based on an anion exchange membrane with a cross-linked structure shows a low PPD difference under high and low relative humidity conditions, so an anion exchange membrane with a cross-linked structure has a higher performance than a conventional anion exchange membrane without a cross-linked structure due to its network structure. It has a high moisture content.
또한, 도 6에는 2.0 V에서 상이한 음이온교환막의 수전해 성능[시험조건: A/C PFBP-14 이오노머, 1M KOH feed, A/C IrO2/Pt/C, (a) 60℃에서 측정한 I-V 곡선, (b) 전기화학 임피던스 분광(EIS) 스펙트럼 및 (c) 80℃에서 측정한 I-V 곡선, (b) 전기화학 임피던스 분광(EIS) 스펙트럼]을 나타내었다.In addition, Figure 6 shows the water electrolysis performance of different anion exchange membranes at 2.0 V [Test conditions: A/C PFBP-14 ionomer, 1M KOH feed, A/C IrO 2 /Pt/C, (a) IV measured at 60°C. curve, (b) electrochemical impedance spectroscopy (EIS) spectrum and (c) IV curve measured at 80°C, (b) electrochemical impedance spectroscopy (EIS) spectrum].
도 6의 데이터로부터 x-PFTP-PS-10 음이온교환막은 수전해 장치에도 적용할 수 있을 것으로 기대된다.From the data in Figure 6, it is expected that the x-PFTP-PS-10 anion exchange membrane can also be applied to water electrolysis devices.
즉, 상용화된 PTFE-Sustainion과 비교하여, x-PFTP-PS-10 음이온교환막 기반의 수전해 장치는 동일한 전압에서 훨씬 더 높은 전류밀도를 갖는다. 구체적으로, x-PFTP-PS-10 음이온교환막 기반의 수전해 장치는 상용화된 PTFE-Sustainion 기반의 수전해 장치보다 약 4배 높은 4 Acm-2의 전류밀도에 해당하는데, 이는 낮은 옴 저항과 전하이동 저항이 주요 원인으로 해석된다.In other words, compared to commercialized PTFE-Sustainion, the x-PFTP-PS-10 anion exchange membrane-based water electrolysis device has a much higher current density at the same voltage. Specifically, the x-PFTP-PS-10 anion exchange membrane-based water electrolysis device corresponds to a current density of 4 Acm -2 , which is about 4 times higher than the commercialized PTFE-Sustainion-based water electrolysis device, which is due to low ohmic resistance and charge. Movement resistance is interpreted as the main cause.
Claims (15)
<화학식 1>
(상기 화학식 1에서, Aryl은 하기 구조식으로 표시되는 화합물로부터 선택되는 상이한 2종의 것이고,
,,,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수)
m, n은 공중합체 이오노머의 반복단위 내 몰분율(%)로서 m>0, n>0, m+n=100이며, p는 20% 이하로 조절된 가교도를 의미한다)A crosslinked poly(aryl piperidinium) copolymer ionomer having a repeating unit represented by <Formula 1> below.
<Formula 1>
(In Formula 1, Aryl is two different types selected from compounds represented by the following structural formulas,
, , , , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10)
m, n are the mole fraction (%) within the repeating unit of the copolymer ionomer, where m>0, n>0, m+n=100, and p means the degree of crosslinking adjusted to 20% or less)
,,,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수) 및 (b) 1-메틸-4-피페리돈을 유기용매에 용해시켜 용액을 형성하는 단계;
(II) 상기 용액에 강산 촉매를 서서히 부가, 교반 및 반응시켜 점성 용액을 얻는 단계;
(III) 상기 점성 용액을 침전, 세척 및 건조하여 고체상의 중합체를 수득하는 단계;
(IV) 상기 고체상의 중합체 및 강산 촉매를 유기용매에 용해시킨 중합체 용액에 K2CO3, 4-비닐벤질클로라이드 및 과량의 할로메탄을 부가 및 반응시켜 스티렌기가 도입된 4급 피페리디늄 염을 형성하는 단계; 및
(V) 중합체 용액을 침전, 세척 및 건조 후, 열처리 하는 단계;를 포함하는 가교 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조방법.(I) as monomers (a) two different types selected from compounds represented by the following structural formula,
, , , , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10) and (b) dissolving 1-methyl-4-piperidone in an organic solvent to form a solution;
(II) slowly adding a strong acid catalyst to the solution, stirring and reacting to obtain a viscous solution;
(III) precipitating, washing and drying the viscous solution to obtain a solid polymer;
(IV) K 2 CO 3 , 4-vinylbenzyl chloride and an excess amount of halomethane were added and reacted to the polymer solution in which the solid polymer and strong acid catalyst were dissolved in an organic solvent to produce a quaternary piperidinium salt into which a styrene group was introduced. forming step; and
(V) Precipitating, washing and drying the polymer solution, followed by heat treatment. A method for producing a cross-linked poly(aryl piperidinium) copolymer ionomer.
(ii) 상기 고분자용액을 유리판에 캐스팅 및 가열함으로써 유기용매를 제거하고 스티렌기 간의 가교반응이 동시에 유도된 막을 수득하는 단계; 및
(iii) 상기 수득한 막을 1M NaHCO3 또는 1M NaOH로 처리한 후, 초순수로 수회 세척 및 건조하는 단계;를 포함하는 음이온교환막의 제조방법.(i) dissolving the cross-linked poly(aryl piperidinium) copolymer ionomer according to claim 1 in an organic solvent to form a polymer solution;
(ii) casting and heating the polymer solution on a glass plate to obtain a film in which the organic solvent is removed and a cross-linking reaction between styrene groups is simultaneously induced; and
(iii) treating the obtained membrane with 1M NaHCO 3 or 1M NaOH, followed by washing and drying several times with ultrapure water.
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| WO2019068051A2 (en) | 2017-09-28 | 2019-04-04 | Yushan Yan | Poly(aryl piperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers |
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| US20190036143A1 (en) | 2016-03-28 | 2019-01-31 | University Of Delaware | Poly(aryl piperidinium) polymers for use as hydroxide exchange membranes and ionomers |
| WO2019068051A2 (en) | 2017-09-28 | 2019-04-04 | Yushan Yan | Poly(aryl piperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers |
| JP2020536165A (en) | 2017-09-28 | 2020-12-10 | ヤン，ユシャン | Poly (arylpiperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers |
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