WO2009066952A1 - Monomer for proton-conducting polymer having acid group in side chain thereof, proton-conducting polymer prepared using the monomer, method of preparing the proton-conducting polymer, electrolyte membrane comprising the proton-conducting polymer, and membrane-electrode assembly including the electrolyte - Google Patents
Monomer for proton-conducting polymer having acid group in side chain thereof, proton-conducting polymer prepared using the monomer, method of preparing the proton-conducting polymer, electrolyte membrane comprising the proton-conducting polymer, and membrane-electrode assembly including the electrolyte Download PDFInfo
- Publication number
- WO2009066952A1 WO2009066952A1 PCT/KR2008/006869 KR2008006869W WO2009066952A1 WO 2009066952 A1 WO2009066952 A1 WO 2009066952A1 KR 2008006869 W KR2008006869 W KR 2008006869W WO 2009066952 A1 WO2009066952 A1 WO 2009066952A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- proton
- conducting polymer
- formula
- electrolyte membrane
- polymer
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 82
- 239000002322 conducting polymer Substances 0.000 title claims abstract description 81
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 81
- 239000003792 electrolyte Substances 0.000 title claims abstract description 58
- 239000002253 acid Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 title abstract description 12
- 229920000642 polymer Polymers 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 21
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 19
- 150000002484 inorganic compounds Chemical class 0.000 claims description 13
- 229910010272 inorganic material Inorganic materials 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 7
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- -1 sulfonated silicon oxide (sulfonated SiO2 Chemical class 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000004693 Polybenzimidazole Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
- 229920002480 polybenzimidazole Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920005649 polyetherethersulfone Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- SBUKLPSBNFWJCU-UHFFFAOYSA-N ClIBr Chemical group ClIBr SBUKLPSBNFWJCU-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 54
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 239000005518 polymer electrolyte Substances 0.000 description 26
- 239000011259 mixed solution Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000446 fuel Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000035699 permeability Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000006277 sulfonation reaction Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 6
- 229920002959 polymer blend Polymers 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 229910021432 inorganic complex Inorganic materials 0.000 description 4
- 229920005597 polymer membrane Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229920005570 flexible polymer Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical class [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- 0 *O*Cc1cc(O)ccc1O Chemical compound *O*Cc1cc(O)ccc1O 0.000 description 1
- JLGADZLAECENGR-UHFFFAOYSA-N 1,1-dibromo-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Br)Br JLGADZLAECENGR-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- WVRJIUQUEYKNPI-UHFFFAOYSA-N 4-(3-bromophenyl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC(Br)=C1 WVRJIUQUEYKNPI-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910004878 Na2S2O4 Inorganic materials 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical group 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/11—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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Definitions
- the present invention relates to a monomer for a proton-conducting polymer, a proton-conducting polymer prepared using the monomer, a method of preparing the proton-conducting polymer, an electrolyte membrane comprising the proton- conducting polymer, and a membrane-electrode assembly including the electrolyte membrane, and more particularly, to a monomer for a proton-conducting polymer, which is used to prepare an electrolyte membrane having excellent structural stability and excellent capability of inhibiting methanol crossover, a proton-conducting polymer prepared using the monomer, a method of preparing the proton-conducting polymer, an electrolyte membrane comprising the proton-conducting polymer, and a membrane- electrode assembly including the electrolyte membrane.
- Polymer electrolyte membrane fuel cells are a type of fuel cells which use a polymer membrane having proton exchange properties as an electrolyte, and are classified into various types, such as, solid polymer electrolyte fuel cells (SPEFCs), or proton exchange membrane fuel cells (PEMFCs). Compared with other types of fuel cells, polymer electrolyte membrane fuel cells (PEMFCs) have a low operating temperature of about 80 0 C , high efficiency, high current density and power density, short start-up time, and quick response characteristics according to load changes.
- SPEFCs solid polymer electrolyte fuel cells
- PEMFCs proton exchange membrane fuel cells
- PEMFCs use a polymer membrane as an electrolyte, there is no corrosion and no need for pH adjustment, and the polymer membrane is less sensitive to a change in the pressure of reactive gases.
- these fuel cells are advantageous due to their simple design, ease of manufacturing, and a wide range of outputs, and thus can be applied to many fields, such as power sources for clean vehicles, on-site power generation, power sources for portable devices, and power sources for military devices.
- Such a fuel cell includes a stack which substantially generates electricity, the stack having a structure in which several to tens of unit cells, each having a membrane- electrode assembly (MEA) and separators (also referred to as 'bipolar plates'), are stacked.
- MEA membrane- electrode assembly
- the MEA is composed of an anode (referred to also as a 'fuel electrode' or an 'oxidation electrode') and a cathode (referred to also as an 'air electrode' or a 'reduction electrode') that are separated by a proton conducting polymer electrolyte membrane.
- a principle of generating electricity in a fuel cell is as follows.
- a fuel is supplied to an anode as a fuel electrode, and absorbed in a catalyst at the anode, and the fuel is oxidized to produce protons and electrons.
- the electrons are transferred to a cathode as an oxidation electrode, via an external circuit, and the protons are transferred to the cathode through a polymer electrolyte membrane.
- An oxidant is supplied to the cathode, and the oxidant, protons, and electrons are reacted on a catalyst at the cathode to produce electricity along with water.
- Characteristics of proton exchange membranes are represented as ion exchange capacity (IEC) or equivalent weight (EW), and properties required for a proton exchange membrane used as an electrolyte membrane for a fuel cell are high proton conductivity and mechanical strength, low gas transmission, and transfer of water. The proton conductivity of the proton exchange membrane is rapidly decreased with dehydration, and thus resistance to dehydration is required. Electrolyte membranes require high resistance to oxidation and reduction reactions and hydrolysis that occur in the electrolyte membrane, good binding with cations, and homogeneity. Such properties should be maintained for a constant time period. In addition to satisfying all the conditions described above, there is a need to develop an inexpensive and environmentally-friendly preparation method in order to commercialize electrolyte membranes.
- a polyimide-based polymer electrolyte, a sulfonated polyimide (S-PI) membrane, is obtained by condensation of diamine having a sulfonic acid group and dianhydride.
- the obtained S-PI membrane has 3 times lower hydrogen gas transmission than that of Nafion 117 and cell performance similar to that of Nafion, whereas lifetime stability of the S-PI membrane is about 3000 hours. This is because chains are disconnected by hydrolysis, thereby decreasing mechanical strength.
- Polysulfones are polymers in which phenyl rings are linked alternately by an ether group and a sulfone (-SO 2 -) group, and are commercially available as poly(arylether sulfone), polysulfone (PSU, Product name: Udel), and polyethersulfone (PES, Product name: Victrex). Even if a degree of sulfonation of sulfonated PSU (S-PSU) is about 30%, the polymer is dissolved in water, and thus a possibility of a use as a fuel cell is low.
- S-PSU degree of sulfonation of sulfonated PSU
- a sulfonated PES (S-PES) polymer membrane is very stable in water, but the membrane needs to have a high degree of sulfonation in order to increase ionic conductivity.
- the higher the degree of sulfonation the weaker the mechanical strength of the electrolyte membrane.
- the conductivity of the S-PES is similar to that of Nafion. In this case, about 400% of swelling occurs, and thus mechanical strength is very low.
- an activated sulfonic acid group is appropriately cross-linked thereto, the swelling can be reduced to about 50%. However, ionic conductivity is also decreased in this case.
- Polyetherketones are polymers in which phenyl groups are linked by ether and carbonyl groups.
- the most commonly-used polyetherketone is polyetheretherketone (PEEK) known as Victrex PEEK.
- PEEK polyetheretherketone
- Victrex PEEK Victrex PEEK
- Sulfonated polyarylene is well known as a commonly-used proton-conducting material.
- Such sulfonated polymers are obtained by polymerizing a general aromatic compound to prepare a polymer, and then reacting the resultant polymer with a sulfonating agent to introduce a sulfonic acid group.
- a sulfonating agent such as concentrated sulfuric acid or funing sulfuric acid
- it is very dangerous when the sulfonated polymers are prepared there is limitation on materials of a plant, and it may not be easy to control the amount and position of introduction of the sulfonic acid group to polymers.
- the present invention provides a monomer for preparing a proton-conducting polymer having an acid group in a side chain.
- the present invention also provides a proton-conducting polymer prepared using the monomer.
- the present invention also provides a method of preparing the proton-conducting polymer.
- the present invention also provides an electrolyte membrane comprising the proton- conducing polymer. [14] The present invention also provides a membrane-electrode assembly including the electrolyte membrane comprising the proton-conducting polymer.
- R 1 is each independently a C 1 -C 10 alkyl group, a C 2 -C 10 alkenyl group, or a phenyl group;
- p is an integer in the range of 0 to 4.
- [20] B is halogen, hydroxyl, or amine
- Y is a bivalent linker comprising at least one of C ! -C 10 alkyl and C 6 -C 20 aryl;
- Z is hydrogen or fluorine
- A is an acid group that can have a proton, and is one selected from a sulfonic acid, sulfonate, a phosphoric acid, and sulfonyl(trifluoro methylsulfonyl).
- a of Formula 1 may be a sulfonic acid or a sulfonate.
- Y of Formula 1 may be one selected from the groups represented by the following formulae: [27]
- R 1 is each independently a Ci-Ci 0 alkyl group, a C 2 -Ci 0 alkenyl group, or a phenyl group;
- the repeating unit of Formula 2 may be represented by Formula 3 below: [40] ⁇ Formula 3>
- a in Formula 2 may be a sulfonic acid or a sulfonate.
- Y in Formula 2 may be one selected from the groups represented by the following structures:
- an electrolyte membrane comprising the proton-conducting polymer of Formula 2.
- the electrolyte membrane may further comprise at least one polymer selected from the group consisting of polyimide, polyetherketone, polysulfone, polyethersulfone, polyetherethersulfone, polybenzimidazole, polyphenylene oxide, poly- phenylenesulfide, polystyrene, polytrifluorostyrene sulfonic acid, polystyrene sulfonic acid, polyurethane, and a branched sulfonated poly(sulfone-ketone) copolymer.
- polyimide polyetherketone
- polysulfone polyethersulfone
- polyetherethersulfone polybenzimidazole
- polyphenylene oxide poly- phenylenesulfide
- polystyrene polytrifluorostyrene sulfonic acid
- polystyrene sulfonic acid polyurethane
- the electrolyte membrane may further comprise at least one inorganic compound selected from the group consisting of silicon oxide (SiO 2 ), titaniun oxide (TiO 2 ), an inorganic phosphate, a sulfonated silicon oxide (sulfonated SiO 2 ), a sulfonated zirconium oxide (sufonated ZrO 2 ), and a sulfonated zirconium phosphate (sulfonated ZrP).
- the electrolyte membrane may further comprise a porous support.
- a membrane- electrode assembly for a fuel cell comprising the electrolyte membrane.
- a polymer electrolyte membrane prepared using a proton-conducting polymer according to an embodiment of the present invention has excellent structural stability and low methanol crossover, and thus a fuel cell including the polymer electrolyte membrane can be prepared, wherein the fuel cell has excellent performance.
- the present invention provides a proton-conducting polymer that has an acid group introduced into a side chain thereof, thereby having excellent proton conductivity and significantly low methanol permeability.
- a proton-conducting polymer that can be used as a high temperature polymer electrolyte such as polysulfone or polyketone
- a high temperature polymer electrolyte such as polysulfone or polyketone
- polysulfone or polyketone due to electron donor properties of an ether group, sulfonation of its main chain is easy, and once the sulfonation of the main chain occurs, the polymer electrolyte has appropriate proton conductivity.
- microphase separation into hydrophilic and hydrophobic regions of the polymer of which the main chain is sulfonated is decreased.
- the proton-conducting polymer forms a flexible polymer chain by introducing an acid group to a side chain instead of a main chain, and has a structure in which mi- crophase separation between hydrophilic and hydrophobic regions can be effectively formed. To form such structure, the proton-conducting polymer has a repeating unit represented by Formula 2 below:
- Y constituting a portion of the side chain is a bivalent linker including C 1 -C 10 alkyl, C 6 -C 20 aryl, or both of them, and may be one selected from the groups represented by the following structures.
- the linker Y is linked to a linear (CZ 2 ) q by an ether bond.
- the side chain may be further extended, whereby the proton-conducting polymer is more flexible and the microphase separation of the proton-conducing polymer may be increased more.
- q controls the length of the side chain, allowing the proton- conducting polymer to have excellent physical properties, and may be an integer in the range of 1 to 10.
- Z is hydrogen or fluorine. To increase acidity of an acid group that can have a proton, Z may be fluorine.
- A is an acid group that can have a proton independently, and is selected from sulfonate represented by -SO 3 H (sulfonic acid) or SO 3 M where M may be Na or K (sulfonate), a phosphoric acid represented by -OPO 3 H, and sulfonyl(trifluoro methylsulfonyl).
- A may be the sulfonic acid or sulfonate, because it has a very high acidity and a C-S bond has a strong resistance to oxidation conditions.
- a hydrogen ion as a cation is attached to an anion of the sulfonic acid, it constitutes a hydrogen ion exchange membrane.
- the conductivity of the hydrogen ion is maintained higher.
- the sulfonic acid group attached to an electrolyte membrane is dissociated into the anion of the sulfonic acid and the hydrogen ion, whereby the hydrogen ion is transferred by concentration gradient or an electric field as in a hydrogen ion in a sulfuric acid electrolyte.
- the proton-conducting polymer represented by Formula 2 may have a nunber average molecular weight of 5,000 to 1,000,000 in terms of mechanical strength and proton conductivity.
- the proton-conducting polymer has a flexible polymer chain by introducing an acid group in its side chain, and the microphase separation of the proton-conducting polymer is also effective.
- An electrolyte membrane comprising the proton-conducting polymer has high proton conductivity and significantly low methanol permeability.
- the proton-conducting polymer may be prepared using a compound represented by
- R 1 is each independently a Ci-Ci 0 alkyl group, a C 2 -Ci 0 alkenyl group, or a phenyl group;
- p is an integer in the range of 0 to 4.
- [81] B is halogen, hydroxyl, or amine
- Y is a bivalent linker including at least one of Ci-Ci 0 alkyl and C 6 -C 20 aryl;
- Z is hydrogen or fluorine
- q is an integer in the range of 1 to 10;
- A is an acid group that can have a proton, and is one selected from a sulfonic acid, sulfonate, a phosphoric acid, and sulfonyl(trifluoro methylsulfonyl).
- the substituent B is linked to a main chain of the proton-conducting polymer and the acid group A that can have a proton is included in a side chain of the proton-conducting polymer.
- the compound of Formula 1 may be a compound represented by Formula 4 below in terms of copolymerizability: [88] ⁇ Formula 4>
- the proton-conducting polymer may be prepared by etherification represented by Reaction Scheme 1 below, but this method is only an exemplary embodiment for preparing the proton-conducting polymer and the preparation method is not limited thereto:
- X in Formula 5 is an activated leaving group, and may be chloro, bromo, or iodine.
- R u P, Y, Z, A, m, and n are the same as defined in Formula 2 above.
- the organic solvent may be any solvent that can satisfactorily dissolve reactants and products, and in particular, may be dimethyl sulfoxide (DMSO), N,N'-dimethylacetamide (DMAc), or N ⁇ nethyl pyrrolidone (NMP).
- DMSO dimethyl sulfoxide
- DMAc N,N'-dimethylacetamide
- NMP N ⁇ nethyl pyrrolidone
- a hydrocarbon- based solvent such as toluene may be further added to the mixed solution, and the organic solvent and the hydrocarbon-based solvent may be mixed in a volume ratio of 3:1.
- an alkaline metal carbonate such as, K 2 CO 3 or Na 2 CO 3 , as a catalyst may be added to the mixed solution.
- the reaction may be performed at a reaction temperature in the range of 100 to 200
- the reaction may be performed such that after stirring is performed at 140-150 0 C for 3 to 5 hours, water in the azeotropic distillate is removed using a dean-stark trap, and after all of the water is removed, the reaction mixture is continuously stirred at 170-190 0 C for 6 to 24 hours. During the reaction, water may be removed by adding toluene to the reaction mixture by using an addition funnel, if necessary.
- the proton-conducting polymer electrolyte membrane may be prepared by dissolving the proton-conducting polymer described above in an organic solvent to prepare an electrolyte membrane forming composition, and then using a general method, such as a solvent casting method or hot pressing method, to form a proton-conducting polymer electrolyte membrane having a desired thickness.
- the thickness of the proton- conducting polymer electrolyte membrane may be in the range of about 5 to about 200 ⁇ m.
- the organic solvent may be a general organic solvent, and in particular, may be the same as the organic solvent used in preparing the proton-conducting polymer described above.
- the proton-conducting polymer electrolyte membrane cast is dried to remove the solvent therefrom, thereby obtaining a film-type proton-conducting polymer electrolyte membrane.
- the drying process is performed by slowly raising the temperature from room temperature up to 80 0 C , drying for 24 hours at 80 0 C , and then further drying at 110 0 C for 24 hours.
- the proton-conducting polymer electrolyte membrane may be prepared by mixing, with an organic solvent, the proton-conducting polymer described above and at least one polymer selected from polyimide, polyetherketone, polysulfone, poly- ethersulfone, polye there thersulf one, polybenzimidazole, polyphenylene oxide, poly- phenylenesulfide, polystyrene, polytrifluorostyrene sulfonic acid, polystyrene sulfonic acid, polyurethane, and branched sulfonated poly(sulfone-ketone) copolymer to prepare a polymer blend composition, and then applying the polymer blend composition to a substrate.
- the amount of the proton-conducting polymer may be in the range of about 1 to about 99 parts by weight based on 100 parts by weight of the total weight of the polymer blend composition.
- the branched sulfonated poly(sulfone-ketone) copolymer refers to a sulfonated poly- sulfoneketone copolymer including an aromatic sulfone repeating unit, an aromatic ketone repeating unit, and a branch unit, as disclosed in Korean Patent No. 2005-0112185 filed by the present applicant, and the disclosure of which is incorporated herein in its entirety by reference.
- the proton-conducting polymer electrolyte membrane may further include an inorganic compound, in addition to the proton-conducting polymer.
- the inorganic compound may be an inorganic metal oxide, such as silicon oxide (SiO 2 ) or titanium oxide (TiO 2 ); an inorganic phosphate, such as zirconium phosphate (Zr(HPO 4 ) 2 • nH 2 0) or phosphotungstic acid (H 3 PW 12 O 4 • nH 2 0); or a sulfonic acid group- substituted inorganic compound, such as a sulfonated silicon oxide (sulfonated SiO 2 ), a sulfonated zirconiun oxide (sufonated ZrO 2 ), or a sulfonated zirconiun phosphate (sulfonated ZrP).
- a sulfonated silicon oxide sulfonated SiO 2
- the sulfonic acid group-substituted inorganic compound introduces an acid group, and thus the conductivity of the proton-conducting polymer electrolyte membrane is increased.
- the inorganic compound to which a sulfonic acid is introduced may be prepared such that ammonia water is dropped on a precursor such as a metal chloride to prepare a colloidal solution of a metal hydride, the colloidal solution thereof is washed and dried, and then a sulfuric acid is added to the resulting particles and the resultant is calcinated at 600 0 C.
- the inorganic compound is dispersed in an organic solvent to prepare a dispersion, and then the dispersion is mixed with a proton-conducting polymer dissolved in an organic solvent.
- the amount of the inorganic compound may be in the range of about 1 to about 99 parts by weight based on 100 parts by weight of the proton-conducting polymer.
- the resultant composition may be cast on a glass plate using the same method as described above to prepare an organic-inorganic complex electrolyte membrane comprising the proton-conducting polymer and the inorganic compound.
- the inorganic compound is dispersed in an organic solvent to prepare a dispersion, and then the dispersion is mixed with a proton-conducting polymer dissolved in an organic solvent.
- the amount of the inorganic compound may be in the range of about 1 to about 99 parts by weight based on 100 parts by weight of the proton-conducting polymer.
- the resultant composition may be cast on a glass plate using the same method as described above to prepare an organic-inorganic complex electrolyte membrane comprising the proton-conducting polymer and the inorganic compound.
- the proton-conducting polymer electrolyte membrane may comprise the proton-conducting polymer and a porous support having a nano-sized particle size.
- the porous support may include at least one selected from the group consisting of silica, alunina, zirconia, zeolite, and titaniun oxide, and the particle size of the porous support is in the range of about 0.1 to about 300 nm.
- the proton-conducting polymer electrolyte membrane comprising the porous support may be prepared using an electrolyte membrane forming composition prepared by dissolving a proton- conducting polymer in an organic solvent to form a mixed solution, and then dispersing a porous support in the mixed solution.
- a membrane-electrode assembly according to an embodiment of the present invention may be prepared by interposing the proton-conducting polymer electrolyte membrane between a cathode and an anode using a general method.
- Example 1 Synthesis of polymer [135]
- Compound 4 (0.01 M), bis(4-chlorophenyl)sulfone (0.05 M), and 4,4'-dihydroxybiphenyl (0.04 M) were dissolved in N ⁇ nethylpyrrolidone (NMP), and then potassiun carbonate (K 2 CO 3 , 0.35 M) and an appropriate amount of toluene were added to the resultant mixed solution.
- NMP N ⁇ nethylpyrrolidone
- K 2 CO 3 , 0.35 M potassiun carbonate
- the temperature of a reactor for reacting the mixed solution was increased to 130 0 C , and the mixed solution was reacted for 4 hours under toluene reflux conditions.
- a polymer electrolyte membrane was prepared in the same manner as in Example 5, except that Nafion 115 was used instead of the polymer of Example 1.
- Proton Conductivity (S/ ⁇ n) (electrolyte membrane thickness (cm) / area (cm 2 )) x initial resistance value (1/ohm) Equation 1.
- the polymer electrolyte membranes of Examples 5 through 10 maintain appropriate proton conductivity, and have much lower methanol permeability than that of the polymer electrolyte membrane of Comparative Example 1. That is, the polymer electrolyte membrane according to an embodiment of the present invention includes an acid group in a side chain thereof, thereby having structural stability due to effective microphase separation, resulting in a reduction in methanol permeability.
Abstract
Provided are a monomer for a proton-conducting polymer having an acid group in aside chain thereof, a proton-conducting polymer prepared using the monomer, a method of preparing the proton-conducting polymer, an electrolyte membrane comprising the proton-conducting polymer, and a membrane-electrode assembly including the electrolyte membrane. The proton-conducting polymer has excellent structural stability and capability of inhibiting methanol crossover
Description
Description
MONOMER FOR PROTON- CONDUCTING POLYMER HAVING ACID GROUP IN SIDE CHAIN THEREOF, PROTON- CONDUCTING POLYMER PREPARED USING THE MONOMER, METHOD OF PREPARING THE PROTON- CONDUCTING POLYMER, ELECTROLYTE MEMBRANE COMPRISING THE PROTON- CONDUCTING POLYMER, AND MEMBRANE-ELECTRODE ASSEMBLY INCLUDING THE
ELECTROLYTE
Technical Field
[1] The present invention relates to a monomer for a proton-conducting polymer, a proton-conducting polymer prepared using the monomer, a method of preparing the proton-conducting polymer, an electrolyte membrane comprising the proton- conducting polymer, and a membrane-electrode assembly including the electrolyte membrane, and more particularly, to a monomer for a proton-conducting polymer, which is used to prepare an electrolyte membrane having excellent structural stability and excellent capability of inhibiting methanol crossover, a proton-conducting polymer prepared using the monomer, a method of preparing the proton-conducting polymer, an electrolyte membrane comprising the proton-conducting polymer, and a membrane- electrode assembly including the electrolyte membrane. Background Art
[2] Polymer electrolyte membrane fuel cells (PEMFCs) are a type of fuel cells which use a polymer membrane having proton exchange properties as an electrolyte, and are classified into various types, such as, solid polymer electrolyte fuel cells (SPEFCs), or proton exchange membrane fuel cells (PEMFCs). Compared with other types of fuel cells, polymer electrolyte membrane fuel cells (PEMFCs) have a low operating temperature of about 80 0C , high efficiency, high current density and power density, short start-up time, and quick response characteristics according to load changes. In particular, since PEMFCs use a polymer membrane as an electrolyte, there is no corrosion and no need for pH adjustment, and the polymer membrane is less sensitive to a change in the pressure of reactive gases. In addition, these fuel cells are advantageous due to their simple design, ease of manufacturing, and a wide range of
outputs, and thus can be applied to many fields, such as power sources for clean vehicles, on-site power generation, power sources for portable devices, and power sources for military devices.
[3] Such a fuel cell includes a stack which substantially generates electricity, the stack having a structure in which several to tens of unit cells, each having a membrane- electrode assembly (MEA) and separators (also referred to as 'bipolar plates'), are stacked. The MEA is composed of an anode (referred to also as a 'fuel electrode' or an 'oxidation electrode') and a cathode (referred to also as an 'air electrode' or a 'reduction electrode') that are separated by a proton conducting polymer electrolyte membrane.
[4] A principle of generating electricity in a fuel cell is as follows. A fuel is supplied to an anode as a fuel electrode, and absorbed in a catalyst at the anode, and the fuel is oxidized to produce protons and electrons. The electrons are transferred to a cathode as an oxidation electrode, via an external circuit, and the protons are transferred to the cathode through a polymer electrolyte membrane. An oxidant is supplied to the cathode, and the oxidant, protons, and electrons are reacted on a catalyst at the cathode to produce electricity along with water.
[5] Characteristics of proton exchange membranes are represented as ion exchange capacity (IEC) or equivalent weight (EW), and properties required for a proton exchange membrane used as an electrolyte membrane for a fuel cell are high proton conductivity and mechanical strength, low gas transmission, and transfer of water. The proton conductivity of the proton exchange membrane is rapidly decreased with dehydration, and thus resistance to dehydration is required. Electrolyte membranes require high resistance to oxidation and reduction reactions and hydrolysis that occur in the electrolyte membrane, good binding with cations, and homogeneity. Such properties should be maintained for a constant time period. In addition to satisfying all the conditions described above, there is a need to develop an inexpensive and environmentally-friendly preparation method in order to commercialize electrolyte membranes.
[6] A polyimide-based polymer electrolyte, a sulfonated polyimide (S-PI) membrane, is obtained by condensation of diamine having a sulfonic acid group and dianhydride. The obtained S-PI membrane has 3 times lower hydrogen gas transmission than that of Nafion 117 and cell performance similar to that of Nafion, whereas lifetime stability of the S-PI membrane is about 3000 hours. This is because chains are disconnected by hydrolysis, thereby decreasing mechanical strength.
[7] Polysulfones are polymers in which phenyl rings are linked alternately by an ether
group and a sulfone (-SO2-) group, and are commercially available as poly(arylether sulfone), polysulfone (PSU, Product name: Udel), and polyethersulfone (PES, Product name: Victrex). Even if a degree of sulfonation of sulfonated PSU (S-PSU) is about 30%, the polymer is dissolved in water, and thus a possibility of a use as a fuel cell is low. A sulfonated PES (S-PES) polymer membrane is very stable in water, but the membrane needs to have a high degree of sulfonation in order to increase ionic conductivity. However, the higher the degree of sulfonation, the weaker the mechanical strength of the electrolyte membrane. When the S-PES has a degree of sulfonation of 90% or greater, the conductivity of the S-PES is similar to that of Nafion. In this case, about 400% of swelling occurs, and thus mechanical strength is very low. To address the problem, if an activated sulfonic acid group is appropriately cross-linked thereto, the swelling can be reduced to about 50%. However, ionic conductivity is also decreased in this case.
[8] Polyetherketones are polymers in which phenyl groups are linked by ether and carbonyl groups. The most commonly-used polyetherketone is polyetheretherketone (PEEK) known as Victrex PEEK. Sulfonated polyarylene is well known as a commonly-used proton-conducting material.
[9] Such sulfonated polymers are obtained by polymerizing a general aromatic compound to prepare a polymer, and then reacting the resultant polymer with a sulfonating agent to introduce a sulfonic acid group. However, since a large amount of the sulfonating agent, such as concentrated sulfuric acid or funing sulfuric acid is used in the introduction of the sulfonic acid group, it is very dangerous when the sulfonated polymers are prepared, there is limitation on materials of a plant, and it may not be easy to control the amount and position of introduction of the sulfonic acid group to polymers.
Disclosure of Invention Technical Problem
[10] The present invention provides a monomer for preparing a proton-conducting polymer having an acid group in a side chain.
[11] The present invention also provides a proton-conducting polymer prepared using the monomer.
[12] The present invention also provides a method of preparing the proton-conducting polymer.
[13] The present invention also provides an electrolyte membrane comprising the proton- conducing polymer.
[14] The present invention also provides a membrane-electrode assembly including the electrolyte membrane comprising the proton-conducting polymer. Technical Solution
[15] According to an aspect of the present invention, there is provided a compound represented by Formula 1 below:
[16] <Formula 1>
[18] wherein R1 is each independently a C1-C10 alkyl group, a C2-C10 alkenyl group, or a phenyl group;
[19] p is an integer in the range of 0 to 4;
[20] B is halogen, hydroxyl, or amine;
[21] Y is a bivalent linker comprising at least one of C !-C10 alkyl and C6-C20 aryl;
[22] Z is hydrogen or fluorine;
[23] q is an integer in the range of 1 to 10; and
[24] A is an acid group that can have a proton, and is one selected from a sulfonic acid, sulfonate, a phosphoric acid, and sulfonyl(trifluoro methylsulfonyl). [25] A of Formula 1 may be a sulfonic acid or a sulfonate.
[26] Y of Formula 1 may be one selected from the groups represented by the following formulae: [27]
[29] <Formula 2>
[31] wherein R1 is each independently a Ci-Ci0 alkyl group, a C2-Ci0 alkenyl group, or a phenyl group;
[32] p is an integer in the range of 0 to 4; [33] Y is a bivalent linker comprising at least one of C i-Ci0 alkyl and C6-C20 aryl; [34] Z is hydrogen or fluorine; [35] q is an integer in the range of 1 to 10; [36] A is an acid group that can have a proton, and is one selected from a sulfonic acid, sulfonate, a phosphoric acid, and sulfonyl(trifluoro methylsulfonyl);
[37] m+n=l, 0<m<l, and 0<n<l; and [38] wherein the proton-conducting polymer has a nunber average molecular weight of about 5,000 to about 1,000,000.
[39] The repeating unit of Formula 2 may be represented by Formula 3 below: [40] <Formula 3>
[42] A in Formula 2 may be a sulfonic acid or a sulfonate. [43] Y in Formula 2 may be one selected from the groups represented by the following structures:
[44]
[45] According to another aspect of the present invention, there is provided a method of preparing the proton-conducting polymer according to claim 4, comprising etheri- fication of compounds represented by Formulae 4 through 6.
[46] <Formula 4>
[48] <Formula 5>
[50] <Formula 6>
[52] wherein X is chloro, bromo, iodine, or fluoro, and [53] R1, A, Y, Z, p, and q are defined as above. [54] According to another aspect of the present invention, there is provided an electrolyte membrane comprising the proton-conducting polymer of Formula 2.
[55] The electrolyte membrane may further comprise at least one polymer selected from the group consisting of polyimide, polyetherketone, polysulfone, polyethersulfone, polyetherethersulfone, polybenzimidazole, polyphenylene oxide, poly- phenylenesulfide, polystyrene, polytrifluorostyrene sulfonic acid, polystyrene sulfonic acid, polyurethane, and a branched sulfonated poly(sulfone-ketone) copolymer.
[56] The electrolyte membrane may further comprise at least one inorganic compound selected from the group consisting of silicon oxide (SiO 2), titaniun oxide (TiO2), an inorganic phosphate, a sulfonated silicon oxide (sulfonated SiO2), a sulfonated zirconium oxide (sufonated ZrO 2), and a sulfonated zirconium phosphate (sulfonated ZrP).
[57] The electrolyte membrane may further comprise a porous support.
[58] According to another aspect of the present invention, there is provided a membrane- electrode assembly for a fuel cell comprising the electrolyte membrane. Advantageous Effects
[59] A polymer electrolyte membrane prepared using a proton-conducting polymer according to an embodiment of the present invention has excellent structural stability and low methanol crossover, and thus a fuel cell including the polymer electrolyte membrane can be prepared, wherein the fuel cell has excellent performance. Mode for Invention
[60] The present invention will now be described in greater detail.
[61] The present invention provides a proton-conducting polymer that has an acid group introduced into a side chain thereof, thereby having excellent proton conductivity and significantly low methanol permeability.
[62] In general, a proton-conducting polymer that can be used as a high temperature polymer electrolyte, such as polysulfone or polyketone, can be inexpensively prepared and has considerable stability under oxidation/reduction conditions at various ranges of temperature. In addition, in such polymer electrolyte, due to electron donor properties of an ether group, sulfonation of its main chain is easy, and once the sulfonation of the main chain occurs, the polymer electrolyte has appropriate proton conductivity. However, microphase separation into hydrophilic and hydrophobic regions of the polymer of which the main chain is sulfonated is decreased. This is because hydrophobic properties of the polymer are decreased due to the presence of an ether group in the main chain of the polymer and/or acidity of a sulfonyl group is decreased due to the ether group. In addition, the decrease in the microphase separation results in a decrease in ionic conductivity and methanol permeability.
[©] The proton-conducting polymer forms a flexible polymer chain by introducing an acid group to a side chain instead of a main chain, and has a structure in which mi- crophase separation between hydrophilic and hydrophobic regions can be effectively formed. To form such structure, the proton-conducting polymer has a repeating unit represented by Formula 2 below:
[64] <Formula 2>
[66] In Formula 2, benzene rings in a main chain may be respectively substituted with 0-4 R1S where each R1 is the same as or different from each other, and may be a C !-C10 alkyl group, a C2-C10 alkenyl group, or a phenyl group. If p=0, that is, if the benzene ring is not substituted with R1 in Formula 2, the repeating unit of Formula 2 may be represented by Formula 3 below:
[67] <Formula 3>
[69] In Formula 2, Y constituting a portion of the side chain is a bivalent linker including C1-C10 alkyl, C6-C20 aryl, or both of them, and may be one selected from the groups represented by the following structures.
[70]
[71] The linker Y is linked to a linear (CZ2)q by an ether bond. As such, the side chain may be further extended, whereby the proton-conducting polymer is more flexible and the microphase separation of the proton-conducing polymer may be increased more. In the formula (CZ 2)q, q controls the length of the side chain, allowing the proton- conducting polymer to have excellent physical properties, and may be an integer in the range of 1 to 10. Z is hydrogen or fluorine. To increase acidity of an acid group that can have a proton, Z may be fluorine.
[72] In Formula 2, A is an acid group that can have a proton independently, and is selected from sulfonate represented by -SO3H (sulfonic acid) or SO3M where M may be Na or K (sulfonate), a phosphoric acid represented by -OPO3H, and sulfonyl(trifluoro methylsulfonyl). In this regard, A may be the sulfonic acid or sulfonate, because it has a very high acidity and a C-S bond has a strong resistance to oxidation conditions. When a hydrogen ion as a cation is attached to an anion of the sulfonic acid, it constitutes a hydrogen ion exchange membrane. In this regard, when water molecules exist together, the conductivity of the hydrogen ion is maintained higher. In the presence of water molecules, the sulfonic acid group attached to an electrolyte membrane is dissociated into the anion of the sulfonic acid and the hydrogen ion, whereby the hydrogen ion is transferred by concentration gradient or an electric field as in a hydrogen ion in a sulfuric acid electrolyte.
[73] In Formula 2, m and n may be appropriately selected to satisfy the conditions m+n=l, 0<m<l, and 0<n<l in order to allow the prepared proton-conducting polymer
to have desirable physical properties, and may be in the range of 0.1<m/(m+n)<10. [74] The proton-conducting polymer represented by Formula 2 may have a nunber average molecular weight of 5,000 to 1,000,000 in terms of mechanical strength and proton conductivity. [75] The proton-conducting polymer has a flexible polymer chain by introducing an acid group in its side chain, and the microphase separation of the proton-conducting polymer is also effective. An electrolyte membrane comprising the proton-conducting polymer has high proton conductivity and significantly low methanol permeability. [76] The proton-conducting polymer may be prepared using a compound represented by
Formula 1 below: [77] <Formula 1>
[79] wherein R1 is each independently a Ci-Ci0 alkyl group, a C2-Ci0 alkenyl group, or a phenyl group;
[80] p is an integer in the range of 0 to 4;
[81] B is halogen, hydroxyl, or amine;
[82] Y is a bivalent linker including at least one of Ci-Ci0 alkyl and C6-C20 aryl;
[83] Z is hydrogen or fluorine;
[84] q is an integer in the range of 1 to 10; and
[85] A is an acid group that can have a proton, and is one selected from a sulfonic acid, sulfonate, a phosphoric acid, and sulfonyl(trifluoro methylsulfonyl). [86] In the proton-conducting polymer prepared using the compound of Formula 1, the substituent B is linked to a main chain of the proton-conducting polymer and the acid group A that can have a proton is included in a side chain of the proton-conducting polymer. [87] The compound of Formula 1 may be a compound represented by Formula 4 below in terms of copolymerizability: [88] <Formula 4>
[89]
2)q-A
[90] In Formula 1, when B is halogen, such as fluoro, chloro, bromo, or iodine, the compound of Formula 1 is substituted with a hydroxyl group using a known method to prepare the compound of Formula 4.
[91] The proton-conducting polymer may be prepared by etherification represented by Reaction Scheme 1 below, but this method is only an exemplary embodiment for preparing the proton-conducting polymer and the preparation method is not limited thereto:
[92] <Reaction Scheme 1>
Formula 2
[94] In Reaction Scheme 1, X in Formula 5 is an activated leaving group, and may be chloro, bromo, or iodine. R u P, Y, Z, A, m, and n are the same as defined in Formula 2 above.
[95] First, compounds represented by Formulae 4, 5, and 6 above are added to an appropriate organic solvent in a ratio of m:m+n:n, to prepare a mixed solution. The organic solvent may be any solvent that can satisfactorily dissolve reactants and products, and in particular, may be dimethyl sulfoxide (DMSO), N,N'-dimethylacetamide (DMAc), or N^nethyl pyrrolidone (NMP). A hydrocarbon-
based solvent, such as toluene may be further added to the mixed solution, and the organic solvent and the hydrocarbon-based solvent may be mixed in a volume ratio of 3:1. In addition, an alkaline metal carbonate, such as, K2CO3 or Na2CO3, as a catalyst may be added to the mixed solution.
[96] The reaction may be performed at a reaction temperature in the range of 100 to 200
0C for 30 minutes to 48 hours in order for the proton-conducting polymer to have a molecular weight in appropriate ranges. The reaction may be performed such that after stirring is performed at 140-150 0C for 3 to 5 hours, water in the azeotropic distillate is removed using a dean-stark trap, and after all of the water is removed, the reaction mixture is continuously stirred at 170-190 0C for 6 to 24 hours. During the reaction, water may be removed by adding toluene to the reaction mixture by using an addition funnel, if necessary.
[97] Hereinafter, a proton-conducting polymer electrolyte membrane according to an embodiment of the present invention will be described.
[98] The proton-conducting polymer electrolyte membrane may be prepared by dissolving the proton-conducting polymer described above in an organic solvent to prepare an electrolyte membrane forming composition, and then using a general method, such as a solvent casting method or hot pressing method, to form a proton-conducting polymer electrolyte membrane having a desired thickness. The thickness of the proton- conducting polymer electrolyte membrane may be in the range of about 5 to about 200 μ m. The organic solvent may be a general organic solvent, and in particular, may be the same as the organic solvent used in preparing the proton-conducting polymer described above. The proton-conducting polymer electrolyte membrane cast is dried to remove the solvent therefrom, thereby obtaining a film-type proton-conducting polymer electrolyte membrane. In this regard, the drying process is performed by slowly raising the temperature from room temperature up to 80 0C , drying for 24 hours at 80 0C , and then further drying at 110 0C for 24 hours.
[99] Alternatively, the proton-conducting polymer electrolyte membrane may be prepared by mixing, with an organic solvent, the proton-conducting polymer described above and at least one polymer selected from polyimide, polyetherketone, polysulfone, poly- ethersulfone, polye there thersulf one, polybenzimidazole, polyphenylene oxide, poly- phenylenesulfide, polystyrene, polytrifluorostyrene sulfonic acid, polystyrene sulfonic acid, polyurethane, and branched sulfonated poly(sulfone-ketone) copolymer to prepare a polymer blend composition, and then applying the polymer blend composition to a substrate. In the preparation of the polymer blend composition, the
amount of the proton-conducting polymer may be in the range of about 1 to about 99 parts by weight based on 100 parts by weight of the total weight of the polymer blend composition.
[100] The branched sulfonated poly(sulfone-ketone) copolymer refers to a sulfonated poly- sulfoneketone copolymer including an aromatic sulfone repeating unit, an aromatic ketone repeating unit, and a branch unit, as disclosed in Korean Patent No. 2005-0112185 filed by the present applicant, and the disclosure of which is incorporated herein in its entirety by reference.
[101] In addition, the proton-conducting polymer electrolyte membrane may further include an inorganic compound, in addition to the proton-conducting polymer. The inorganic compound may be an inorganic metal oxide, such as silicon oxide (SiO 2) or titanium oxide (TiO2); an inorganic phosphate, such as zirconium phosphate (Zr(HPO4) 2 • nH20) or phosphotungstic acid (H3PW12O4 • nH20); or a sulfonic acid group- substituted inorganic compound, such as a sulfonated silicon oxide (sulfonated SiO 2), a sulfonated zirconiun oxide (sufonated ZrO 2), or a sulfonated zirconiun phosphate (sulfonated ZrP).
[102] In particular, the sulfonic acid group-substituted inorganic compound introduces an acid group, and thus the conductivity of the proton-conducting polymer electrolyte membrane is increased. The inorganic compound to which a sulfonic acid is introduced may be prepared such that ammonia water is dropped on a precursor such as a metal chloride to prepare a colloidal solution of a metal hydride, the colloidal solution thereof is washed and dried, and then a sulfuric acid is added to the resulting particles and the resultant is calcinated at 600 0C.
[103] The inorganic compound is dispersed in an organic solvent to prepare a dispersion, and then the dispersion is mixed with a proton-conducting polymer dissolved in an organic solvent. The amount of the inorganic compound may be in the range of about 1 to about 99 parts by weight based on 100 parts by weight of the proton-conducting polymer. Next, the resultant composition may be cast on a glass plate using the same method as described above to prepare an organic-inorganic complex electrolyte membrane comprising the proton-conducting polymer and the inorganic compound.
[104] The inorganic compound is dispersed in an organic solvent to prepare a dispersion, and then the dispersion is mixed with a proton-conducting polymer dissolved in an organic solvent. The amount of the inorganic compound may be in the range of about 1 to about 99 parts by weight based on 100 parts by weight of the proton-conducting polymer. Next, the resultant composition may be cast on a glass plate using the same
method as described above to prepare an organic-inorganic complex electrolyte membrane comprising the proton-conducting polymer and the inorganic compound.
[105] In addition, the proton-conducting polymer electrolyte membrane may comprise the proton-conducting polymer and a porous support having a nano-sized particle size. The porous support may include at least one selected from the group consisting of silica, alunina, zirconia, zeolite, and titaniun oxide, and the particle size of the porous support is in the range of about 0.1 to about 300 nm. The proton-conducting polymer electrolyte membrane comprising the porous support may be prepared using an electrolyte membrane forming composition prepared by dissolving a proton- conducting polymer in an organic solvent to form a mixed solution, and then dispersing a porous support in the mixed solution.
[106] A membrane-electrode assembly according to an embodiment of the present invention may be prepared by interposing the proton-conducting polymer electrolyte membrane between a cathode and an anode using a general method.
[107] The present invention will now be described in greater detail with reference to the following examples. The following examples are for illustrative purposes and are not intended to limit the scope of the invention.
[108] Example
[109] <Synthesis Example>
[110] First, Compound 4 is synthesized through Reaction Scheme 2.
[I l l] <Reaction Scheme 2>
[113] ( 1 ) Synthesis of Compound 1
[114] 3 equivalent weight of dimethoxybenzene was dissolved in 250 ml of THF, and then
3.3 equivalent weight of n-butyllithiun was slowly added to the nixed solution using an addition funnel. Then, 1 equivalent weight of 4-bromo-(4'-hydroxyphenyl)benzene was slowly added to the reaction solution through the addition funnel. After the reaction solution was cooled to room temperature, the reaction was terminated with 300 ml of IM hydrochloric acid and the organic product was extracted using di- ethylether. Then, the organic layer containing the organic product was washed several times using a NaCl solution, and then moisture was removed therefrom using magnesiun sulfate. Then, the resultant product was separated using a colunn chromatography (yield: 82%) to obtain Compound 1.
[115] NMR and mass analysis results of the separated product are as follows.
[116] IH NMR: 7.45-6.79 (rnJ lH), 3.81(s,3H), 3.77(s,3H)
[117] Mass: 306(M+, 100), 291(28), 276(21), 260(16)
[118] (2) Synthesis of Compound 2
[119] The prepared Compound 1 (1 equivalent weight) and NaH (1.2 equivalent weight) were dissolved in 100 ml of dimethylsulfoxide and the mixture was reacted at room temperature for 1 hour. Then, 2 equivalent weight of dibromotetrafluoroethane was added to the resultant reaction solution and the resultant was further reacted for 4 hours. The reaction was terminated with a saturated NaCl solution, and then an organic compound was extracted using dimethylether. Then, the resultant product was separated by column chromatography (yield: 89%) to obtain Compound 2.
[120] IH NMR: 7.5-6.83 (m, 1 IH), 3.78 (s,3H), 3.74(s,3H)
[121] 19F NMR: -Θ8.47(t, J= 4Hz, 2F), -86.30(t, J=4Hz, 2F)
[122] (3) Synthesis of Compound 3
[123] BBr3 was slowly added dropwise to a solution in which the obtained Compound 2 (1 equivalent weight) was dissolved in chloroform and the mixture was reacted at room temperature for 4 hours. Then, distilled water was added to the reaction mixture to terminate the reaction. An organic layer was collected from the resultant and a solvent was removed therefrom to obtain Compound 3.
[124] IH NMR: 7.61-6.74 (m, 1 IH)
[125] 19F NMR: -68.51(S, J= 2F), -86.32(S, J=2F)
[126] Mass: 458(M+2, 100), 456(M+, 100), 256(18), 231(43), 202(40), 189(25), 176(19), 165(37), 131(27), 82(33)
[127] (4) Synthesis of Compound 4
[128] The obtained Compound 3 (1 eg.), Na2S2O4 (4 eg.), and NaHCO 3 (1 eg.) were dissolved in a mixed solvent of dimethylsulfoxide (DMSO) and distilled water, and
then the nixed solution was reacted at 80 0C for 3 hours, and the reaction solution was cooled to room temperature. Then, an organic layer was extracted using ethylacetate. After removal of a solvent, the reaction mixture was dissolved in distilled water, hydrogen peroxide was added to the resultant and the reaction solution was further reacted for 2 hours. NaCl was added to the resultant reaction solution and then a precipitate was filtered to obtain Compound 4.
[129] 19F-NMR: -80(S, 2F), -116.06(S, 2F) [130] <Preparation of polymer for polymer electrolyte membrane> [131] A method of preparing a polymer using the obtained Compound 4 in Examples 1 through 4 below will now be described.
[132] <Reaction Scheme 3>
[134] Example 1 : Synthesis of polymer [135] Compound 4 (0.01 M), bis(4-chlorophenyl)sulfone (0.05 M), and 4,4'-dihydroxybiphenyl (0.04 M) were dissolved in N^nethylpyrrolidone (NMP), and then potassiun carbonate (K2CO3, 0.35 M) and an appropriate amount of toluene were added to the resultant mixed solution. The temperature of a reactor for reacting the mixed solution was increased to 130 0C , and the mixed solution was reacted for 4 hours under toluene reflux conditions. Then, the toluene was removed and the resultant was further reacted at 180 0C for 18 hours to complete the synthesis of a polymer. The polymer was purified by isopropyl alcohol precipitation.
[136] Example 2: Synthesis of polymer
[137] Compound 4 (0.015 M), bis(4-chlorophenyl)sulfone (0.05 M), and
4,4'-dihydroxybiphenyl (0.035 M) were dissolved in Nmethylpyrrolidone (NMP), and then potassiun carbonate (K2CO3, 0.35 M) and an appropriate amount of toluene were added to the resultant mixed solution. The temperature of a reactor for reacting the mixed solution was increased to 130 0C , the mixed solution was reacted for 4 hours under toluene reflux conditions. Then, the toluene was removed and the resultant was further reacted at 180 0C for 18 hours to complete the synthesis of a polymer. The polymer was purified by isopropyl alcohol precipitation.
[138] Example 3: Synthesis of polymer
[139] Compound 4 (0.02 M), bis(4-chlorophenyl)sulfone (0.05 M), and
4,4'-dihydroxybiphenyl (0.03 M) were dissolved in N^nethylpyrrolidone (NMP), and then potassiun carbonate (K2CO3, 0.35 M) and an appropriate amount of toluene were added to the resultant mixed solution. The temperature of a reactor for reacting the mixed solution was increased to 130 0C , and the mixed solution was reacted for 4 hours under toluene reflux conditions. Then, the toluene was removed and the resultant was further reacted at 180 0C for 18 hours to complete the synthesis of a polymer. The polymer was purified by isopropyl alcohol precipitation.
[140] Example 4: Synthesis of polymer
[141] Compound 4 (0.025 M), bis(4-chlorophenyl)sulfone (0.05 M), and
4,4'-dihydroxybiphenyl (0.025 M) were dissolved in N^nethylpyrrolidone (NMP), and then potassiun carbonate (K2CO3, 0.35 M) and an appropriate amount of toluene were added to the resultant mixed solution. The temperature of a reactor for reacting the mixed solution was increased to 130 0C , and the mixed solution was reacted for 4 hours under toluene reflux conditions. Then, the toluene was removed and the resultant was further reacted at 180 0C for 18 hours to complete the synthesis of a polymer. The polymer was purified by isopropyl alcohol precipitation.
[142] <Preparation of polymer electrolyte membrane>
[143] Hereinafter, a method of preparing a polymer electrolyte membrane will be described.
[144] Examples 5-8: Preparation of polymer electrolyte membrane
[145] 1 g of each of the polymers prepared in Examples 1 through 4 was dissolved in N- methylpyrrolidone (NMP), and then the resultant mixed solution was cast on a glass plate. Then, the resultant was heated at 6O0C for 3 hours and dried in a vacuum at 12O0Cf or 24 hours. As a result, polymer electrolyte membranes having sulfonation
degrees different from each other were obtained.
[146] Example 9: Preparation of polymer blend electrolyte membrane
[147] 1 g of the polymer prepared in Example 4 and 0.3 g of sulfonated polyethereth- erketone were dissolved in 10 ml of N^nethylpyrrolidone, and then the resultant mixed solution was cast on a glass plate. Then, the resultant was heated at 60 0C for 3 hours and dried in a vacuum at 120 0C for 24 hours to obtain a polymer blend electrolyte membrane.
[148] Example 10: Preparation of organic-inorganic complex electrolyte membrane
[149] 1 g of the polymer prepared in Example 4 and 0.05 g of silicon oxide were dissolved in 10 ml of N^nethylpyrrolidone, and then the resultant mixed solution was cast on a glass plate. Then, the resultant was heated at 6O0C for 3 hours and dried in a vacuun at 120°Cfor 24 hours to obtain an organic-inorganic complex electrolyte membrane.
[150] Comparative Example 1 : Preparation of polymer electrolyte membrane
[151] A polymer electrolyte membrane was prepared in the same manner as in Example 5, except that Nafion 115 was used instead of the polymer of Example 1.
[152] <Evaluation of polymer electrolyte membrane>
[153] (1) Proton conductivity
[154] Each of the polymer electrolyte membranes prepared in Examples 5 through 10 and Comparative Example 1 was interposed between electrodes each having an area of 2.54 cm2, and then an initial resistance of each polymer electrolyte membrane was measured at 30 0C using a potentiometer. The proton conductivity of the polymer electrolyte membranes was measured using Equation 1 below. The obtained proton conductivities are shown in Table 1.
[155] Proton Conductivity (S/αn) = (electrolyte membrane thickness (cm) / area (cm 2)) x initial resistance value (1/ohm) Equation 1.
[156] (2) Methanol Permeability
[157] Methanol permeating cells were prepared, and each of the polymer electrolyte membranes prepared in Examples 5 through 10 and Comparative Example 1 was interposed between the methanol permeating cells, and the assemblies were fixed to each other using an epoxy adhesive. 15 ml of a IM aqueous methanol solution was added to one of the cells, and 15 ml of distilled water was added to the other thereof. Then, 10 id of the resultant solution was collected from the cell including the distilled water once every 10 minutes, and 10 id of distilled water was added to the collected solution to maintain the volume thereof constant. The methanol concentration of the collected sample was measured by gas chromatography. A change in methanol concentration
according to time was measured to produce a graph, and the methanol permeability of each polymer electrolyte membrane was measured from a slope of the graph by using Equation 2 below. The results are shown in Table 1 below.
[158] Methanol Permeability (an 2/S) = [slope (ppm/s) x solution volune (an 3) x electrolyte membrane thickness (an)] / [electrolyte membrane area (cm 2) x methanol concentration (ppm)] Equation 2.
[159] In Equation 2, the solution volume, electrolyte membrane area and methanol concentration were respectively maintained constant at 15αn 3, 7.06αn2, and 1M=32OOO ppm.
[160] <Table 1> [161] [Table 1] [Table ]
[162] Referring to Table 1, the polymer electrolyte membranes of Examples 5 through 10 maintain appropriate proton conductivity, and have much lower methanol permeability than that of the polymer electrolyte membrane of Comparative Example 1. That is, the polymer electrolyte membrane according to an embodiment of the present invention includes an acid group in a side chain thereof, thereby having structural stability due to effective microphase separation, resulting in a reduction in methanol permeability.
[163] While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the
following claims.
Claims
[1] A compound represented by Formula 1 below: <Formula 1>
Y is a bivalent linker comprising at least one of C i-Ci0 alkyl and C6-C20 aryl; Z is hydrogen or fluorine; q is an integer in the range of 1 to 10; and
A is an acid group that can have a proton, and is one selected from a sulfonic acid, sulfonate, a phosphoric acid, and sulfonyl(trifluoro methylsulfonyl).
[2] The compound of claim 1, wherein A is a sulfonic acid or a sulfonate.
[3] The compound of claim 1, wherein Y is one selected from the groups represented by the following formulae:
[4] A proton-conducting polymer comprising a repeating unit represented by Formula 2 below:
<Formula 2>
Y is a bivalent linker comprising at least one of C i-Ci0 alkyl and C6-C20 aryl;
Z is hydrogen or fluorine; q is an integer in the range of 1 to 10;
A is an acid group that can have a proton, and is one selected from a sulfonic acid, sulfonate, a phosphoric acid, and sulfonyl(trifluoro methylsulfonyl); m+n=l, 0<m<l, and 0<n<l; and wherein the proton-conducting polymer has a nunber average molecular weight of about 5,000 to about 1,000,000.
[5] The proton-conducting polymer of claim 4, wherein the repeating unit of
Formula 2 is represented by Formula 3 below:
<Formula 3>
[6] The proton-conducting polymer of claim 4, wherein A is a sulfonic acid or a sulfonate.
[7] The proton-conducting polymer of claim 4, wherein Y is one selected from the groups represented by the following structures:
[8] A method of preparing the proton-conducting polymer according to claim 4, comprising etherification of compounds represented by Formulae 4 through 6.
<Formula 4>
<Formula 5>
wherein X is chloro, bromo, iodine, or fluoro, and
R1, A, Y, Z, p, and q are the same as defined in claim 4.
[9] An electrolyte membrane comprising the proton-conducting polymer according to claim 4.
[10] The electrolyte membrane of claim 9, further comprising at least one polymer selected from the group consisting of polyimide, polyetherketone, polysulfone, polyethersulfone, polye there thersulf one, polybenzimidazole, polyphenylene oxide, polyphenylenesulfide, polystyrene, polytrifluorostyrene sulfonic acid, polystyrene sulfonic acid, polyurethane, and a branched sulfonated poly(sulfone-ketone) copolymer.
[11] The electrolyte membrane of claim 9, further comprising at least one inorganic compound selected from the group consisting of silicon oxide (SiO 2), titaniun oxide (TiO2), an inorganic phosphate, a sulfonated silicon oxide (sulfonated SiO2 ), a sulfonated zirconiun oxide (sufonated ZrO2), and a sulfonated zirconiun phosphate (sulfonated ZrP).
[12] The electrolyte membrane of claim 9, further comprising a porous support.
[13] A membrane-electrode assembly comprising the electrolyte membrane according to any one of claims 9 through 12.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070120364A KR20090053499A (en) | 2007-11-23 | 2007-11-23 | Monomer for a proton-conducting polymer having acid group in side chain, the proton-conducting polymer, preparation method of the polymer, membrane comprising the polymer and membrane-electrode assembly employing the membrane |
| KR10-2007-0120364 | 2007-11-23 |
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| WO2009066952A1 true WO2009066952A1 (en) | 2009-05-28 |
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| PCT/KR2008/006869 WO2009066952A1 (en) | 2007-11-23 | 2008-11-21 | Monomer for proton-conducting polymer having acid group in side chain thereof, proton-conducting polymer prepared using the monomer, method of preparing the proton-conducting polymer, electrolyte membrane comprising the proton-conducting polymer, and membrane-electrode assembly including the electrolyte |
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| WO (1) | WO2009066952A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013085463A1 (en) * | 2011-12-09 | 2013-06-13 | Shogo Takamuku | Polymeric material comprising ortho-positioned acidic groups |
| EP2786999B1 (en) * | 2011-12-02 | 2018-02-07 | LG Chem, Ltd. | Sulphonate based compound, polymer electrolyte membrane comprising same and fuel cell comprising same |
| JP2018528983A (en) * | 2015-09-22 | 2018-10-04 | エルジー・ケム・リミテッド | Block polymer and polymer electrolyte membrane containing the same |
| JP2019516809A (en) * | 2016-03-29 | 2019-06-20 | エルジー・ケム・リミテッド | Block polymer and polymer electrolyte membrane containing the same |
| WO2021033482A1 (en) * | 2019-08-19 | 2021-02-25 | Jsr株式会社 | Dispersion composition, dispersant, anisotropic film and method for producing same, and apparatus for forming anisotropic film |
| CN115020771A (en) * | 2022-05-07 | 2022-09-06 | 中国地质大学（武汉） | HBM blending modification-based PBI proton exchange membrane and preparation method and application thereof |
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| KR101272940B1 (en) * | 2011-09-29 | 2013-06-12 | 주식회사 동진쎄미켐 | Proton-conducting polymer and uses thereof |
| KR101947605B1 (en) * | 2015-01-26 | 2019-02-14 | 주식회사 엘지화학 | Halogenated compound, polymer and polymer electrolyte membrane using the same |
| KR101839184B1 (en) * | 2015-01-27 | 2018-03-15 | 주식회사 엘지화학 | Polymer and polymer electrolyte membrane using the same |
| WO2017052226A1 (en) * | 2015-09-22 | 2017-03-30 | 주식회사 엘지화학 | Block polymer and polymer electrolyte membrane including same |
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| US20010041279A1 (en) * | 1999-12-27 | 2001-11-15 | Atsushi Terahara | Polymer electrolyte and method for producing the same |
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| US20010041279A1 (en) * | 1999-12-27 | 2001-11-15 | Atsushi Terahara | Polymer electrolyte and method for producing the same |
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| EP2786999B1 (en) * | 2011-12-02 | 2018-02-07 | LG Chem, Ltd. | Sulphonate based compound, polymer electrolyte membrane comprising same and fuel cell comprising same |
| WO2013085463A1 (en) * | 2011-12-09 | 2013-06-13 | Shogo Takamuku | Polymeric material comprising ortho-positioned acidic groups |
| JP2018528983A (en) * | 2015-09-22 | 2018-10-04 | エルジー・ケム・リミテッド | Block polymer and polymer electrolyte membrane containing the same |
| JP2019516809A (en) * | 2016-03-29 | 2019-06-20 | エルジー・ケム・リミテッド | Block polymer and polymer electrolyte membrane containing the same |
| US11637306B2 (en) * | 2017-06-29 | 2023-04-25 | Kolon Industries, Inc. | Membrane-electrode assembly, method for manufacturing same, and fuel cell comprising same |
| WO2021033482A1 (en) * | 2019-08-19 | 2021-02-25 | Jsr株式会社 | Dispersion composition, dispersant, anisotropic film and method for producing same, and apparatus for forming anisotropic film |
| CN114026178A (en) * | 2019-08-19 | 2022-02-08 | Jsr株式会社 | Dispersion composition, dispersant, anisotropic film and method for producing same, and anisotropic film forming apparatus |
| CN114026178B (en) * | 2019-08-19 | 2024-01-30 | Jsr株式会社 | Dispersing composition, dispersing agent, anisotropic film, method for producing the same, and anisotropic film forming apparatus |
| CN115020771A (en) * | 2022-05-07 | 2022-09-06 | 中国地质大学（武汉） | HBM blending modification-based PBI proton exchange membrane and preparation method and application thereof |
| CN115020771B (en) * | 2022-05-07 | 2024-03-15 | 中国地质大学（武汉） | HBM blending modified PBI proton exchange membrane and preparation method and application thereof |
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