CN1326917C - 质子导电膜及其应用 - Google Patents
质子导电膜及其应用 Download PDFInfo
- Publication number
- CN1326917C CN1326917C CNB038202387A CN03820238A CN1326917C CN 1326917 C CN1326917 C CN 1326917C CN B038202387 A CNB038202387 A CN B038202387A CN 03820238 A CN03820238 A CN 03820238A CN 1326917 C CN1326917 C CN 1326917C
- Authority
- CN
- China
- Prior art keywords
- acid
- film
- dicarboxylic acid
- benzene
- fragrance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000012528 membrane Substances 0.000 title claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000000446 fuel Substances 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 19
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 4
- 239000002322 conducting polymer Substances 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 43
- 239000003205 fragrance Substances 0.000 claims description 33
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 27
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 23
- 229920000128 polypyrrole Polymers 0.000 claims description 22
- 238000006277 sulfonation reaction Methods 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- -1 amino m benzene dicarboxylic acid Chemical compound 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 12
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 125000002252 acyl group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical group C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims description 3
- SQJQLYOMPSJVQS-UHFFFAOYSA-N 4-(4-carboxyphenyl)sulfonylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C=C1 SQJQLYOMPSJVQS-UHFFFAOYSA-N 0.000 claims description 3
- XFFZVIRSYFJKEX-UHFFFAOYSA-N 4-phenylpyridine-2,5-dicarboxylic acid Chemical compound C1=NC(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O XFFZVIRSYFJKEX-UHFFFAOYSA-N 0.000 claims description 3
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- HLRLQGYRJSKVNX-UHFFFAOYSA-N pyrimidine-2,4-dicarboxylic acid Chemical compound OC(=O)C1=CC=NC(C(O)=O)=N1 HLRLQGYRJSKVNX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 2
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 claims description 2
- NXRWBYFOLHCASC-UHFFFAOYSA-N 2-[carboxy-(carboxymethylamino)methyl]benzoic acid Chemical compound OC(=O)CNC(C(O)=O)C1=CC=CC=C1C(O)=O NXRWBYFOLHCASC-UHFFFAOYSA-N 0.000 claims description 2
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical group C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 claims description 2
- AQBVAFIJSHZDBS-UHFFFAOYSA-N 4-(3,4-diaminophenyl)benzene-1,2-diamine propane Chemical compound CCC.NC=1C=C(C=CC1N)C1=CC(=C(C=C1)N)N AQBVAFIJSHZDBS-UHFFFAOYSA-N 0.000 claims description 2
- ULRYKCILDSQBMT-UHFFFAOYSA-N 4-(3,4-diaminophenyl)benzene-1,2-diamine;methane Chemical compound C.C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 ULRYKCILDSQBMT-UHFFFAOYSA-N 0.000 claims description 2
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 claims description 2
- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 claims description 2
- NLNRQJQXCQVDQJ-UHFFFAOYSA-N bis(3,4-diaminophenyl)methanone Chemical compound C1=C(N)C(N)=CC=C1C(=O)C1=CC=C(N)C(N)=C1 NLNRQJQXCQVDQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 229960004979 fampridine Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000001261 hydroxy acids Chemical class 0.000 claims description 2
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- MJIVRKPEXXHNJT-UHFFFAOYSA-N lutidinic acid Chemical compound OC(=O)C1=CC=NC(C(O)=O)=C1 MJIVRKPEXXHNJT-UHFFFAOYSA-N 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- GMIOYJQLNFNGPR-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CN=C(C(O)=O)C=N1 GMIOYJQLNFNGPR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- MMHLSHSAOIJBHI-UHFFFAOYSA-N 5-(3-carboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 MMHLSHSAOIJBHI-UHFFFAOYSA-N 0.000 claims 1
- LQEZHWGJSWHXPJ-UHFFFAOYSA-N 5-(4-carboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C(O)=O)=CC(C(O)=O)=C1 LQEZHWGJSWHXPJ-UHFFFAOYSA-N 0.000 claims 1
- 229920000388 Polyphosphate Polymers 0.000 claims 1
- 125000005354 acylalkyl group Chemical group 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000002843 carboxylic acid group Chemical group 0.000 claims 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 claims 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 claims 1
- 239000001205 polyphosphate Substances 0.000 claims 1
- 235000011176 polyphosphates Nutrition 0.000 claims 1
- CHGYKYXGIWNSCD-UHFFFAOYSA-N pyridine-2,4,6-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=NC(C(O)=O)=C1 CHGYKYXGIWNSCD-UHFFFAOYSA-N 0.000 claims 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 claims 1
- 229960000368 sulisobenzone Drugs 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000005518 polymer electrolyte Substances 0.000 abstract description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 29
- 229920002480 polybenzimidazole Polymers 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- 210000004027 cell Anatomy 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 235000011007 phosphoric acid Nutrition 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 11
- 238000002047 photoemission electron microscopy Methods 0.000 description 10
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 10
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
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- 150000003233 pyrroles Chemical class 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 3
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- 230000008901 benefit Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
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- 229910052697 platinum Inorganic materials 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- FCBJLBCGHCTPAQ-UHFFFAOYSA-N 1-fluorobutane Chemical compound CCCCF FCBJLBCGHCTPAQ-UHFFFAOYSA-N 0.000 description 2
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- DBFNNZPHSUROFB-UHFFFAOYSA-N 4-amino-N-fluorobenzenesulfonamide Chemical compound S(=O)(C1=CC=C(C=C1)N)(=O)NF DBFNNZPHSUROFB-UHFFFAOYSA-N 0.000 description 2
- HKDYKRFXYCKBCZ-UHFFFAOYSA-N 5-phenylbenzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1 HKDYKRFXYCKBCZ-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
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- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
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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
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- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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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
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- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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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
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- C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明涉及含有磺酸基的芳香聚吡咯基新型质子导电聚合物膜,其中磺酸基共价结合到聚合物的芳香环上,由于其优异的化学和热性质而可用于许多的应用场合。这样的材料特别用于制备PEM燃料电池的聚合物电解质膜(PEM)。
Description
本发明涉及含有磺酸基团的芳香类聚吡咯基新型质子导电性聚合物膜,其中的磺酸基团键合到聚合物的芳香环上,且由于其优异的化学和热性质而可以多种方式使用。这类材料特别是用作制备PEM燃料电池中聚合物电解质膜(PEMs)。
聚合物电解质燃料电池(PEMFCs)是基于质子导电性聚合物膜作为电解质,即,聚合物电解质膜。此时燃料电池包括串联的多个独立的膜电极单元(MEUs)。这种MEU组成的PEM的两侧均安装有电极,且在膜和电解的界面上负载有重金属催化剂,通常为铂。电池中的电化学反应发生在催化剂的三相边界处(燃料气体/催化剂/聚和物电解质)。富氢燃料如氢气、甲醇、或天然气用作阳极处的燃料。富氧气体,通常为空气,被供应至相对的阴极侧。这种方式下燃料电池的化学能直接转变成电能和热。形成反应产物水。在这种构造中,PEM产生主要功能。因此,其对于两种燃料必须具有低渗透性,从而作为隔离膜,其作为电解质也必须具有高的质子导电性,同时其也必须具有高的机械性能、化学和热稳定性,从而能够在温度高达200℃的强酸性介质中长时间使用而不会失效。电池性能及其稳定性从而与膜的质量息息相关。
燃料电池中所用的电解质为固态如聚合物电解质膜、陶瓷氧化物、熔融碳酸盐;或液态如磷酸或氢氧化钾溶液。最近,聚合物电极质膜已被关注作为燃料电池的电解质。大体上,可分为两类聚合物电解质膜。
第一类包括阳离子交换膜,其包括含有键合的酸基团的聚合物结构,优选磺酸基团。
磺酸基团释放氢离子后被转变成阴离子,从而能够质子导电。质子的移动能力和质子导电性直接与水含量有关。如果膜干燥,例如由于高温,膜的导电性以及相应的电池能力会急剧下降。含有阳离子交换膜的燃料电池的工作温度从而被限制在水的沸点以内。而用作聚合物电解质膜的材料为,例如,全氟磺酸聚合物。所述全氟磺酸聚合物(例如萘烷)通常具有全氟烃骨架例如四氟乙烯和三氟乙烯基和带有磺酸基团的侧链(例如连接在全氟烷基上且带有磺酸基的侧链)的共聚物。
已经得到发展的第二类包括这样的聚合物电解质膜,其包括碱性聚合物和强酸的络合物。因此,WO 96/13872和相应的美国专利5525436描述了制备质子导电性聚合物电解质膜的方法,其中碱性聚合物(如聚吡咯)可用强酸如磷酸、磺酸等进行处理。
聚吡啶如聚苯并咪唑(Celazole)很久以前就为人们所知。此类聚苯并咪唑的制备通过是令3,3’,4,4’-四氨基联苯与间苯二羧酸或二苯基间苯二羧酸或其酯在熔融状态下反应。该形成的预聚物在反应器中固化然后被机械粉碎。然后粉碎的聚合物在高至400℃温度下进行固相聚合以完全聚合得到所需聚苯并咪唑。
为制备聚合物膜,PBI在另外的步骤中溶解于极性的,质子惰性的溶剂如二甲基乙酰胺(DMAc)中并以经典方法制备膜。
在另外的步骤中,碱性聚合物或聚合物混合物膜用强酸漫渍或掺杂。为此,碱性聚合物或聚合物混合物膜被浸入强酸,优选磷酸,从而膜被强酸浸渍,且变成质子导电膜。
J.Electrochem.Soc.Volume 142,No.7,1995,pp.L121-123中描述了这种在磷酸中掺杂聚苯并吡咯的方法。
用于PEM燃料电池的质子导电的,即酸掺杂的聚吡咯膜是已知的。掺杂的碱性聚吡咯膜然后在聚合物电解质膜燃料电池中(PEM燃料电池)作为质子导体和分隔物。
由于聚吡咯聚合物的优异性能,这样的聚合物电解质膜可以在转化为膜电极单元(MEUs)后用于燃料电池中,并在高于100℃,特别是高于120℃的条件下连续工作。这一高的连续操作温度使得存在于膜电极单元(MEU)中的贵金属所产生的活性得到提高。特别是在使用烃重整产物时,重整气中存在大量一氧化碳,这些一氧化碳通常需要通过复杂的气体处理或气体精制除去。能够提高操作温度使得它可以在长期操作中耐受明显更高的CO杂质浓度。
使用基于聚吡咯聚合物的聚合物电解质膜首先可以在某些情况下省略复杂的气体处理或气体精制步骤,且还可使负载于膜电极单元中的催化剂的量减少。二者对于PEM燃料电极的大规模使用均是不可或缺的必要条件,否则会使PEM燃料电池系统的成本过高。
已知基于聚吡咯的酸掺杂聚合物膜表现了良好的总体性能。但是这些性能还需要整体的提高以使PEM燃料电池可用于需要的应用中,特别是对于汽车业和分散供电及产热(固定应用)。另外,迄今已知聚合物膜具有高含量的二甲基乙酰胺(DMAc),其无法通过已知干燥方法完全除去。德国专利申请No.10109829.4描述了基于聚吡咯的聚合物膜,其中的DMAc杂质被除去。尽管这样的聚合物膜表现了改善的机械性能,其比导电率不超过0.1S/cm(于140℃)。
这种用磷酸掺杂膜的显著优点在于该体系可在温度高于100℃下运行,而不需要在其他情况下所必需的使电池湿润。这是由于根据“Grotthus原理”(K.-D.Kreuer,Chem.Mater.1996,8,610-641)不需添加水磷酸可传输质子。这种无水传输机理用在直接甲醇燃料电池中特别有意义。此时所用的燃料为甲醇,其可被直接氧化而不需要预重整步骤。为了实现无水质子传输,甲醇不随迁移的质子传输,其中质子迁移是以水合外层的形式进行,其通常以“Vehicle”机理进行(K.-D.Kreuer,Chem.Mater.1996,8,610-641)。直接甲醇燃料电池的动力和效率可通过降低甲醇的“交叉”而得到提高。
在温度高于100℃的条件下运行可产生燃料电池系统的另外的优点。首先,Pt催化剂对气体中杂质(特别是CO)的敏感性被大大降低,催化活性被提高。CO是包括烃化合物(例如天然气、甲醇或汽油)的富氢气体重整时形成的副产品,或是甲醇直接氧化的中间产物。在温度低于100℃时燃料中CO的含量通常低于100ppm。但是,当温度在150-200℃时,可容许10000ppm或更高的CO(N.J.Bjerrum et al.,Journal of Applied Electrochemistry,2001,31,773-779)。这大大简化了上游的重整步骤,从而降低了整个燃料电池系统的成本。
除了上述通过集成方法制备的酸掺杂聚合物膜,包括碱性聚合物的聚合物电解质膜也可直接由多磷酸制备。为此,德国申请号10117686.4中描述的起始单体、或德国申请号10144815.5中描述的预聚物、或德国申请号10117687.2中描述的不熔化性起始聚合物溶解在多磷酸中,随后扩展,不需要随后的处理如干燥、洗涤和掺杂便可直接通过刮片用作质子导电膜。这种方法的主要优点是简单。另外,可通过单体的目标选择,特制得到新类型的聚合物电解质膜。
除了上述提及的材料,从现有技术中也已知制备磺化聚合物的相应方法。
为了从聚醚酮制备PEM,PEK聚合物首先溶解在适当的溶剂中,如高浓度硫酸,然后加入聚集的(aggressive)磺化剂如发烟硫酸或氯磺酸。这种磺化聚合物可在后续步骤中从磺化溶液中分离。为进一步处理,然后通过后续步骤中的碱性溶液,其可被转变成中性盐形式。聚合物随后进入溶液,且在进一步的处理步骤中,借助刮刀通过膜浇铸或铺展制备聚合物膜。溶剂,优选N-甲基吡咯烷酮或N-二甲基乙酰胺通过干燥蒸发。然后用酸对膜再次进行处理,随后进行洗涤直至中性。可替换的方式,通过挤出或膜浇铸、随后用辐照接枝法改性而预先制备的聚合物膜如苯乙烯改性、部分氟化的膜可用磺化溶液进行处理,其中磺化溶液中包括氯磺酸和无水溶剂,如四氯乙烷(EP-A-667983,DE-A-19844645)。
在这些使用强磺化剂进行的磺化处理中,在聚合物许多位置都会发生未受控制的磺化。该磺化也可导致链断裂,从而损害其机械性能,最终导致燃料电池的过早失效。
文献中也公开了磺化的聚苯并咪唑。因此,US-A-4634530描述了在温度高达100℃时用磺化试剂如硫酸或发烟硫酸来磺化未掺杂的聚苯并咪唑膜。
另外,Staiti et al.(P.Staiti in J.Membr.Sci.188(2001)71)已经公开了磺化聚苯并咪唑的制备和性质。此时没有必要在溶液中进行聚合物的磺化。向PBI/DMAc中加入磺化试剂后,聚合物沉淀。为了进行磺化,首先制备PBI膜,且将其浸入稀释的硫酸中。然后在约475℃下处理2分钟以进行磺化。磺化的PBI膜在160℃下的最大电导率为7.5*10-5S/cm。最大离子交换容量为0.12-meq/g。同样也表明这类磺化PBI膜不适合用在燃料电池中。
US-A-4997892描述了通过羟基乙基改性的PBI与磺内酯反应制备硫代烷基化PBI膜。根据该技术,其可制备硫代丙基化PBI膜(Sanuiet al.in polymer.Adv.Techn.11(2000)544)。这类膜的质子导电性为10-3S/cm,其太低而不能用在需要0.1S/cm的燃料电池中。
本发明的目的是提供磺化且高温稳定的聚合物膜,其甚至在高的操作温度下也具有高的导电性。该目的可通过提供包括用磷酸掺杂的磺化聚吡咯的聚合物电解质膜。聚吡咯的磺化通过在制备聚吡咯的聚合反应过程中或之后立即加入适当的磺化剂来实现。
本发明提供的磺化聚吡咯基质子导电聚合物膜得自以下步骤:
A)将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体含有至少两个酸基的芳香羧酸或其酯混合,或将一种或多种芳香和/或杂芳香二氨基羧酸混入多磷酸/磺化剂混合物中形成溶液和/或分散液,
B)使用步骤A中得到的混合物涂覆一层至载体或电极上,
C)将步骤B描述的所得片状结构/层在惰性气体下加热至高达350℃,优选高至280℃以制备聚吡咯聚合物,
D)对步骤C所得膜进行处理至其可以自支撑。
本发明所用芳香及杂芳香四氨基化合物优选为3,3’,4,4’-四氨基联苯,2,3,5,6-四氨基吡啶,1,2,4,5-四氨基苯,双(3,4-二氨基苯基)砜,双(3,4-二氨基苯基)醚,3,3’,4,4’-四氨基苯甲酮,3,3’,4,4’-四氨基联苯甲烷和3,3’,4,4’-四氨基联苯二甲基甲烷及其盐,特别是它们的单-氯化氢衍生物,二-氯化氢衍生物,三-氯化氢衍生物及四氯化氢衍生物。
步骤A)所用芳香羧酸特别地为二羧酸和三羧酸及四羧酸或其酯或酐。术语芳香羧酸还包括杂芳香羧酸。芳香二羧酸优选为间苯二羧酸,对苯二羧酸,苯二羧酸,5-羟基间苯二羧酸,4-羟基间苯二羧酸,2-羟基对苯二羧酸,5-氨基间苯二羧酸,5-N,N-二甲基氨基间苯二羧酸,5-N,N-二乙基氨基间苯二羧酸,2,5-二羟基对苯二羧酸,2,6-二羟基间苯二羧酸,4,6-二羟基间苯二羧酸,2,3-二羟基邻苯二羧酸,2,4-二羟基邻苯二羧酸;3,4-二羟基邻苯二羧酸,3-氟邻苯二羧酸,5-氟间苯二羧酸,2-氟对苯二羧酸,四氟邻苯二羧酸,四氟间苯二羧酸,四氟对苯二羧酸,1,4-萘二羧酸,1,5-萘二羧酸,2,6-萘二羧酸,2,7-萘二羧酸,联苯甲酸,1,8-二羟基萘-3,6-二羧酸,双(4-羧苯基)醚,苯甲酮-4,4’-二羧酸,双(4-羧苯基)砜,联苯-4,4’二羧茇,4-三氟甲基邻苯二羧酸,2,2-双(4-羧苯基)六氟丙烷,4,4’-芪二羧酸,4-羧基肉桂酸或其C1-C20烷基酯或C5-C12芳基酯或它们的酸酐或它们的氯代酰基。芳香三羧酸或四羧酸及其C1-C20烷基酯或C5-C12芳基酯或它们的酸酐或它们的氯代酰基优选为1,3,5-苯三羧酸(苯均三羧酸),1,2,4-苯三羧酸(苯偏三羧酸),(2-羧苯基)亚氨基二乙酸,3,5,3’-联苯三羧酸,3,5,4’-联苯三羧酸。
芳香四羧酸或其C1-C20烷基酯或C5-C12芳基酯或它们的酸酐或它们的氯代酰基优选为3,5,3’,5’-联苯四羧酸,1,2,4,5-苯四羧酸,苯甲酮四羧酸,3,3’,4,4’-联苯四羧酸,2,2’,3,3’-联苯四羧酸,1,2,5,6-萘四羧酸,1,4,5,8-萘四羧酸。
本发明所用杂芳香酸为杂芳香二羧酸和三羟酸或四羧酸或其酯或酐。对于本发明,杂芳香酸的芳香系统在芳香部分含有至少一个氮,氧,硫或磷原子。优选为吡啶-2,5-二羧酸,吡啶-3,5-二羧酸,吡啶-2,6-二羧酸,吡啶-2,4-二羧酸,4-苯基-2,5-吡啶-二羧酸,3,5-吡唑二羧酸,2,6-嘧啶二羧酸,2,5-吡嗪二羧酸,2,4,6-吡啶三羧酸,苯并咪唑-5,6-二羧酸,及其C1-C20烷基酯或C5-C12芳基酯或它们的酸酐或它们的氯代酰基。
三羧酸或四羧酸的含量(基于所用二羧酸)为0-30mol%,优选0.1-20mol%,特别是0.5-10mol%。
根据本发明所用芳香或杂芳香二氨基羧酸优选为二氨基苯甲酸及其单氯化氢和二氯化氢衍生物。
步骤A)中所用多磷酸为市售多磷酸直接使用,如购自Riedel-deHaen。多磷酸Hn+2PnO3n+1(n>1)通常以P2O5量计算的分析值(酸滴定)为至少83%。不作为单体的溶液,还可能制备分散液/悬浮液。步骤A)中所得混合物中多磷酸与单体总量的重量比为1∶10000至10000∶1,优选1∶1000至1000∶1,更优选1∶100至100∶1。
步骤A)中的磺化剂可为i)浓缩硫酸(>95%),ii)氯磺酸,iii)SO3与路易斯碱或其它有机组分的络合物;iv)酰基或烷基硫酸酯;v)有机磺酸;或vi)i~v的混合物。
所用磺化剂的量基于多磷酸为1-20wt%、优选为2-15wt%、特别优选为5-10wt%。
步骤B)中所得薄层由已知的制备聚合物膜现有技术中的方法(铸塑,喷塑,刮刀涂抹)制备。对于载体,可使用在所使用条件下为惰性的任何载体。为调节粘度,溶液可以,如果需要,与磷酸混合(浓缩磷酸,85%)。通过此方法,粘度可调节至所需值且更易于形成膜。步骤B)中所得薄层厚度为20至4000μm,优选30至3500μm,更优选50至3000μm。
步骤C)所得聚吡咯基聚合物含有重复的式(I)和/或(II)和/或(III)和/或(IV)和/或(V)和/或(VI)和/或(VII)和/或(VIII)和/或(IX)和/或(X)和/或(XI)和/或(XII)和/或(XIII)和/或(XIV)和/或(XV)和/或(XVI)和/或(XVI)和/或(XVII)和/或(XVIII)和/或(XIX)和/或(XX)和/或(XXI)和/或(XXII)的吡咯单元。
其中
Ar相同或不同地,各自为四价芳香或杂芳香基团,具有一个或多个环,
Ar1相同或不同地,各自为二价芳香或杂芳香基团,具有一个或多个环,
Ar2相同或不同地,各自为二价或三价芳香或杂芳香基团,具有一个或多个环,
Ar3相同或不同地,各自为三价芳香或杂芳香基团,具有一个或多个环,
Ar4相同或不同地,各自为三价芳香或杂芳香基团,具有一个或多个环,
Ar5相同或不同地,各自为四价芳香或杂芳香基团,具有一个或多个环,
Ar6相同或不同地,各自为二价芳香或杂芳香基团,具有一个或多个环,
Ar7相同或不同地,各自为二价芳香或杂芳香基团,具有一个或多个环,
Ar8相同或不同地,各自为三价芳香或杂芳香基团,具有一个或多个环,
Ar9相同或不同地,各自为二价或三价或四价芳香或杂芳香基团,具有一个或多个环,
Ar10相同或不同地,各自为二价或三价芳香或杂芳香基团,具有一个或多个环,
Ar11相同或不同地,各自为二价芳香或杂芳香基团,具有一个或多个环,
X相同或不同地,各自为氧,硫,或含有一个氢原子的氨基,含有1-20个碳原子的基团,优选带或不带支链的烷基或烷氧基,或芳基作为另外的基团。
R相同或不同地,各自为氢,烷基或芳基且
n,m各自为大于或等于10的整数,优选大于或等于100,
且含硫量为2-20wt%(通过元素分析来确定),特别为4-10wt%。
优选芳香或杂芳香基团衍生自苯,萘,联苯,联苯醚,联苯甲烷,联苯二甲基甲烷,双苯基酮,联苯砜,喹啉,吡啶,双吡啶,哒嗪,嘧啶,吡嗪,三嗪,四嗪,吡咯,吡唑,蒽,苯并吡咯,苯并三唑,苯并氧硫二唑,苯并氧二唑,苯并吡啶,苯并吡嗪,苯并哒嗪,苯并嘧啶,苯并吡嗪,苯并三嗪,中氮茚,喹嗪,吡啶并吡啶,咪唑并嘧啶,吡嗪并嘧啶,咔唑,吖啶,吩嗪,苯并喹啉,吩 嗪,吩噻嗪,二苯并哒嗪(acridizine),苯并蝶啶,菲咯啉和菲,它们也可以是取代的。
Ar1,Ar4,Ar6,Ar7,Ar8,Ar9,Ar10,Ar11,可为任何形式的取代;例如对于亚苯基,Ar1,Ar4,Ar6,Ar7,Ar8,Ar9,Ar10,Ar11各自可为邻、间或对亚苯基。特别优选衍生自苯和联苯的基团,其也可为取代的。
优选烷基为具有1至4个碳的短链烷基,如甲基,乙基,正丙基或异丙基及叔丁基。
优选芳基为苯基或萘基。烷基和芳基可为取代的。
优选取代基为卤原子如氟,氨基,羟基或短链烷基如甲基或乙基。
优选具有如式(I)重复单元的聚吡咯,其中重复单元中的X基团是相同的。
原则上聚吡咯可含有不同重复单元,其不同之处在于基团X是不同的。但是,优选它们在重复单元中仅含有相同的基团X。
另外,优选聚吡咯聚合物为聚咪唑,聚苯并噻唑,聚苯并唑,聚二唑,聚喹啉,聚噻二唑,聚(吡啶),聚(嘧啶),和聚(tetrazapyrenes)。
在本发明另一个实施方案中,含有重复的吡咯单元的聚合物是共聚物或含有至少两个彼此不同的式(I)至式(XXII)单元的混合物。聚合物可以是嵌段共聚物(二嵌段,三嵌段),无规共聚物,周期共聚物和/或交替聚合物。
在本发明一个特别优选的实施方案中,含有重复吡咯单元的聚合物是仅含有式(I)和/或式(II)单元的聚吡咯。
重复的吡咯单元的数量优选大于或等于10。特别优选聚合物含有至少100个重复的吡咯单元。
对于本发明,优选含有重复苯并咪唑单元的聚合物。一些特别有利的聚合物的实例含有重复的如下通式的苯并咪唑单元:
其中n和m各自为大于或等于10的整数,优选大于或等于100。
如上方法所得聚吡咯,特别是聚苯并咪唑,具有高分子量。测量其本征粘度,至少为1.4dl/g,因而显著高于市售苯并咪唑(IV<1.1dl/g)。
如果步骤A)所得混合物含有三羧酸或四羧酸,可通过此方法可形成所得聚合物的分枝或交联。这使得机械性能改善。步骤C)所得聚合物薄层在有水汽条件下于高温下处理,时间足以使薄层的强度足以用于燃料电池中。处理可持续至膜可以自支撑,从而其可从载体上剥离而不产生破坏。
在本方法的一个变化中,齐聚物和/或聚合物的形成可通过将步骤A)所得混合物加热至高达350℃,优选高至280℃得到。取决于所选温度和时间,步骤C)中的热处理可部分或全部省去。这一变化也是本发明的一个目的。
另外,已发现当使用芳香二羧酸(或杂芳香二羧酸)如间苯二羧酸,对苯二羧酸,2,5-二羟基对苯二羧酸,4,6-二羟基间苯二羧酸,2,6-二羟基间苯二羧酸,联苯甲酸,1,8-二羟基萘-3,6-二羧酸,双(4-羧苯基)醚,苯甲酮-4,4’-二羧酸,双(4-羧苯基)砜,联苯-4,4’-二羧酸,4-三氟甲基邻苯二羧酸,吡啶-2,5-二羧酸,吡啶-3,5-二羧酸,吡啶-2,6-二羧酸,吡啶-2,4-二羧酸,4-苯基-2,5-吡啶-二羧酸,3,5-吡唑二羧酸,2,6-嘧啶二羧酸,2,5-吡嗪二羧酸时,如果希望在此步骤中形成齐聚物和/或聚合物,步骤C)或步骤A)中的温度范围高至300℃,优选为100-250℃是有利的。
步骤D)中膜的处理是在高于0℃并低于150℃的温度下进行,优选温度范围为10-120℃,特别优选室温(20℃)至90℃,存在水汽或水和/或水蒸气。处理优选在常压下进行,但也可在高压下进行。重要的是处理需在足量水存在下进行以使多磷酸有助于强化膜,这是部分水解形成低分子量多磷酸和/或磷酸的结果。
步骤D)中多磷酸的部分水解导致膜的强化并使膜厚降低,形成厚度为15至3000μm,优选20至2000μm,更优选20至1500μm的自撑膜。步骤B)中所得多磷酸薄层的分子内及分子间结构在步骤C)中导致有序膜的形成,其对应于所形成膜的特殊性质。
步骤D)中处理温度的上限通常为150℃。如果水汽存在时间极短,如使用过热蒸汽时,蒸汽温度也可能高于150℃。选定处理温度上限的一个重要参数是处理时间。
部分水解(步骤D)也可在控温并控湿的室中进行,从而水解可以在指定量水汽存在下控制在指定的方式下进行。此时水汽量可通过温度或与膜接触的饱和环境,如气体如空气,氮气,二氧化碳或其他适合气体,或蒸汽,以预定的方式设定。处理时间取决于所选上述参数。处理时间取决于膜厚。
处理时间通常从几秒到几分钟,如在过热蒸汽作用下,或多至几天,如在空气中在室温下及较低的相对湿度下。处理时间优选为10秒至300小时,特别是1分钟至200小时。
如果部分水解在室温(20℃)下使用相对湿度为40-80%的空气进行,处理时间为1至200小时。
步骤D)中用水处理也可进行到磷酸完全从膜中被除去的程度。
步骤D)中所得膜可制成自撑的,即其可从载体上剥离而不产生破坏并在需要时立即进行随后的处理。
磷酸浓度及本发明聚合物膜的导电性可通过水解程度设定,即,时间,温度和环境湿度水平。根据本发明,磷酸浓度为每摩尔聚合物重复单元的酸的摩尔数。对于本发明,浓度(每摩尔式(III),即聚苯并咪唑重复单元的磷酸的摩尔数)为10至50,优选12至40。这样高浓度的掺杂(浓度)在使用市售正磷酸掺杂聚咪唑时是非常困难或不可能的。
经过上述步骤D)处理之后,膜可在空气中氧存在下通过加热在表面进行交联。这一对膜表面的硬化处理进一步改善了膜的性质。交联也可通过IR或NIR(IR=红外,即波长长于700nm的光;NIR=近红外,即波长范围为700-2000nm或能量范围为0.6-1.75eV的光)完成。另一种方法是通过β射线照射。此时照射的剂量范围为5至200kGy。
本发明聚合物膜与迄今已知的掺杂的聚合物膜相比具有改善的材料性质。特别地,其与已知的掺杂的聚合物膜相比具有改善的性能。这是由于,特别地,在高于室温且低于100℃时膜不被湿润的条件下,质子传导性能得到提高。在室温和120℃时的电导均至少为0.06S/cm,优选为至少0.08S/cm,更优选至少0.09S/cm。
为进一步提高使用性质,可另外向膜中添加填充剂,特别是质子导电填充剂,及另外的酸。添加可在步骤A中或聚合之后进行。
非限制性的质子导电填充剂的例子为:
硫酸盐,CsHSO4,Fe(SO4)2,(NH4)3H(SO4)2,LiHSO4,NaHSO4,KHSO4,
RbSO4,LiN2H5SO4,NH4HSO4,
磷酸盐,如Zr3(PO4)4,Zr(HPO4)2,HZr2(PO4)3,UO2PO4·3H2O,H8UO2PO4,
Ce(HPO4)2,Ti(HPO4)2,KH2PO4,NaH2PO4,LiH2PO4,
NH4H2PO4,CsH2PO4,CaHPO4,MgHPO4,HSbP2O8,
HSb3P2O14,H5Sb5P2O20,
多酸,H3PW12O40·nH2O(n=21-29),H3SiW12O40·nH2O(n=21-29),
HxWO3,HSbWO6,H3PMo12O40,H2Sb4O11,HTaWO8,
HNbO3,HTiNbO5,HTiTaO5,HSbTeO6,H5Ti4O9,HSbO3,
H2MoO4,
亚硒酸盐和砷酸盐,(NH4)3H(SeO4)2,UO2AsO4,(NH4)3H(SeO4)2,
KH2AsO4,Cs3H(SeO4)2,Rb3H(SeO4)2,
氧化物,如:Al2O3,Sb2O5,ThO2,SnO2,ZrO2,MoO3,
硅酸盐,如沸石,沸石(NH4+),片状硅酸盐,网状硅酸盐,H-钠沸石,H-丝光沸石,NH4-方沸石,NH4-方钠石,没食子酸铵盐,H-蒙脱石;
酸,如HclO4,SbF5
填充剂如碳化物,特别是SiC,Si3N4,纤维,特别是玻璃纤维,玻璃粉和/或聚合物纤维,优选基于聚吡咯者。
这些膜还可含有全氟代磺酸添加剂(0.1-20wt%,优选0.2-15wt%,更优选0.2-10wt%)。这些添加剂使性能改善,在阴极附近增加氧的溶解性和氧的扩散性并降低铂上磷酸和磷酸盐的吸附。(磷酸燃料电池中的电极添加剂,Gang,Xiao;Hjuler,H.A.;Olsen,C.;Berg,R.W.;Bjerrum,N.J..Chem.Dep.A,Tech.Univ.Denmark,Lyngby,Den.J.Electrochem.Soc.(1993),140(4),896-902,及以全氟代磺胺作为磷酸燃料电池中的添加剂.Razaq,M.;Razaq,A.;Yeager,E.;DesMarteau,Darryl D.;Singh,S.Case Cent.Electrochem.Sci.,Case West.ReserveUniv.,Cleveland,OH,USA.J.Electrochem.Soc.(1989),136(2),385-90)。
全氟代磺酸添加剂的非限制性的例子为:
三氟甲烷磺酸,三氟甲烷磺酸钾,三氟甲烷磺酸钠,三氟甲烷磺酸锂,三氟甲烷磺酸铵,全氟代己烷磺酸钾,全氟代己烷磺酸钠,全氟代己烷磺酸锂,全氟代己烷磺酸铵,全氟代己烷磺酸,非氟代丁烷磺酸钾,非氟代丁烷磺酸钠,非氟代丁烷磺酸锂,非氟代丁烷磺酸铵,非氟代丁烷磺酸铯,全氟代己烷磺酸三乙铵,全氟代磺胺和Nafion。
而且,膜可进一步含有可清除(主抗氧剂)或破坏(副抗氧剂)操作中还原氧时产生的过氧化物残基的添加剂并进而提高膜和膜电极的寿命和稳定性,如JP20001118591 A2所述。这样的添加剂的分子结构及其发挥作用的方式述于F.Gugumus在Plastics Additives,HanserVerlag,1990;N.S.Allen,M.Edge Fundamentals of polymer Degradationand Stability,Elsevier,1992;或H.Zweifel,Stabilization of PolymericMaterials,Springer,1998.这样的添加剂的非限制性的例子为:双(三氟甲基)硝基氧,2,2-二苯基-1-苦味碱基偕腙肼,苯酚,烷基酚,立体位阻的烷基酚如Irganox,芳香胺,立体位阻的胺如Chimassorb;立体位阻的羟胺,立体位阻的烷基胺,立体位阻的羟胺,立体位阻的羟胺醚,亚磷酸盐如Irgafos,亚硝基苯,甲基-2-亚硝基丙烷,苯甲酮,苯甲醛叔丁基硝酮,半胱胺,三聚氰胺,铅氧化物,锰氧化物,镍氧化物,钴氧化物。
本发明掺杂的聚合物膜可能的应用领域包括,尤其是,用于燃料电池,电解,电容及电池系统。由于其性质,掺杂的聚合物膜优选用于燃料电池。
本发明还涉及膜电极单元,其含有至少一个本发明的聚合物膜。关于膜电极单元的进一步信息,可参考专家的文献,特别是专利US-A-4,191,618,US-A-4,212,714和US-A-4,333,805。上述参考文献中[US-A-4,191,618,US-A-4,212,714和US-A-4,333,805]涉及膜电极单元和电极的结构和制备,气体扩散层及可选择的催化剂的公开引入本说明中作为参考文献。
在本发明的一个变化中,膜可直接在电极上而不是在载体上形成。这样步骤D)中的处理可以缩短,因为膜不再需要是自支撑的。这样的膜也是本发明的一个目的。
聚合/齐聚物的形成也可在步骤A)中进行且溶液可通过刮刀涂抹涂覆于电极上。然后步骤C)可部分或完全省去。
上述变化及优选实施方案也将应用于本主题,所以关于此点的重复部分在此省略。
步骤D)之后的涂层厚度为2至3000μm,优选3至2000μm,更优选5至1500μm。
通过此方法涂覆的电极可引入膜电极单元中,膜电极单元,如果需要,可以含有至少一个本发明的聚合物膜。
通用测试方法:
IEC的测定方法
膜的导电率高度依赖于以离子交换能力(IEC)表征的酸基团的含量。为测量离子交换能力,刻下直径为3cm的样本并置于充满100ml水的烧杯中。所释出的酸用0.1M的NaOH滴定。然后取出样本,掸去过量水并于160℃将样本干燥4小时。用重量法精确测量干重mo至0.1mg。根据下式由至第一滴定终点的0.1M NaOH消耗量,V1ml,和干重momg计算离子交换能力:
IEC=V1X300/m。
比导电率的测定方法
在恒电势模式下用铂电极(导线直径为0.25mm)通过以四极排列的阻抗谱进行测量比导电率。集电极的间距为2cm。所得谱用由平行排列的欧姆电阻和电容以简单模式评估。膜用磷酸掺杂的样本截面于样本要安装前进行测量。为测量与温度关系,将测量池放置在设定于所需温度的烘箱中,温度用放置在紧邻样本处的Pt-100电阻温度计进行调节。达到所需温度后,样本在开始测量前于该温度下保持10分钟。
实施例
用于制备原位磺化PBI膜的储备溶液
938.6g多磷酸(83.4土0.5%P2O5)加入1.51三颈瓶中的26.948g间苯二羧酸,34.74g 3,3’,4,4’-四氨基联苯的混合物中,三颈瓶配备N2入口与出口和机械搅拌器。混合物加热至120℃保持2小时,然后是150℃3小时,然后是180℃2小时最后是220℃14小时。所得浓度为5%的PBI在PPA中的溶液冷却至RT并用于制备下述磺化的PBI膜。
小部分溶液用水沉淀。沉淀的树脂过滤,用水洗涤三次,用氢氧化铵中和,然后用水洗涤并在100℃,0.001bar干燥16小时。用浓度为0.4%的在100ml浓度为96%硫酸中的PBI溶液测量本征粘度ηint,所得值为ηint=1.52dl/g。
样品1:(PPA/1sPBI膜)
在220℃下,将22.34g浓度为85%的磷酸和1.66g浓度为96%的硫酸加入到100g在浓度为113.6%的PPA中的浓度为5%的PBI储存溶液中,混合30分钟。该溶液在220℃下再搅拌4小时。在220℃下,将得到的在PPA中的磺化PBI溶液通过预热的刮片(381μm)涂覆到玻璃片上。可得到透明膜。该膜然后在RT下保持1天得到可自支撑的膜。
样品2:(PPA/2sPBI膜)
在220℃下,将17.24g浓度为85%的磷酸和3.314g浓度为96%的硫酸加入到100g在浓度为113.6%的PPA中浓度为5%的PBI储存溶液中,混合30分钟。该溶液在220℃下再搅拌4小时。在220℃下,将得到的在PPA中的磺化PBI溶液通过预热的刮片(381μm)涂覆到玻璃片上。可得到透明膜。该膜然后在RT下保持1天。
样品3:(PPA/3sPBI膜)
在220℃下,将24.76g浓度为85%的磷酸和4.97g浓度为96%的硫酸加入到100g在浓度为113.6%的PPA中的浓度为5%的PBI储存溶液中,混和30分钟。该溶液在220℃下再搅拌4小时。在220℃下,将得到的在PPA中的磺化PBI溶液通过预热的刮片(381μm)涂覆到玻璃片上。可得到透明膜。该膜然后在RT下保持1天。
样品4:(PPA/4sPBI膜)
在220℃下,将38.89g浓度为85%的磷酸和6.6288g浓度为96%的硫酸加入到100g在浓度为113.6%的PPA中的浓度为5%的PBI储存溶液中,混合30分钟。该溶液在220℃下再搅拌4小时。在220℃下,将得到的在浓度为105.1%的PPA中的磺化PBI溶液通过预热的刮片(381μm)涂覆到玻璃片上。可得到透明膜。该膜然后在RT下保持1天得到可自支撑的膜。
样品5:(PPA/6sPBI膜)
在220℃下,将41.22g浓度为85%的磷酸和19.333g浓度为96%的硫酸加入到100g在浓度为113.6%的PPA中的浓度为5%的PBI储存溶液中,混和30分钟。该溶液在220℃下再搅拌4小时。在220℃下,将得到的在PPA中的磺化PBI溶液通过预热的刮片(381μm)涂覆到玻璃片上。可得到透明膜。该膜然后在RT下保持1天。
表:IEC及导电率结果
厚度 | IV | S含量 | SO3H含量 | H3PO4含量 | IEC | IEC | 在RT下 | 在120℃下 | |
样品 | [μm] | [dl/g] | [%] | [%] | [%] | [meq/g] | [eq/cm3] | σ(S/cm) | σ(S/cm) |
1 | 210 | 1.14 | 4.16 | 14.4 | 14.23 | 138.56 | 2.5 | 0.092 | 0.064 |
2 | 231 | 1.16 | 6.22 | 21.5 | 15.71 | 153.01 | 3.21 | 0.083 | 0.082 |
3 | 186 | 1.1 | 8.49 | 29.4 | 20.16 | 196.36 | 3.16 | 0.099 | 0.054 |
4 | 184 | 1.14 | 8.95 | 30.6 | 19.78 | 192.66 | 3.14 | 0.09 | 0.089 |
5 | 218 | 1.14 | 9.16 | 31.7 | 23.08 | 224.76 | 3.22 | 0.096 | 0.092 |
Claims (31)
1.一种基于磺化的含有重复苯并咪唑单元聚合物的质子导电聚合物膜,由包括以下步骤的方法得到:
A)将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体含有至少两个酸基的芳香羧酸或其酯,或将一种或多种芳香和/或杂芳香二氨基羧酸,混入多磷酸/磺化剂混合物中形成溶液和/或分散液,
B)将步骤A中的混合物涂覆一层至载体上,
C)将步骤B描述的所得片状结构/层在惰性气体在高达350℃下加热以制备聚吡咯聚合物,
D)在水份存在下并在一定的温度下对步骤C所得聚合物层进行处理一定的时间直到膜可自支撑,而且可与载体分离而不破坏。
2.如权利要求1的膜,特征在于所述的载体为电极。
3.如权利要求1的膜,特征在于步骤C)中的加热温度高至280℃。
4.如权利要求1的膜,特征在于所用芳香四氨基化合物为3,3’,4,4’-四氨基联苯,2,3,5,6-四氨基吡啶,1,2,4,5-四氨基苯,双(3,4-二氨基苯基)砜,双(3,4-二氨基苯基)醚,3,3’,4,4’-四氨基苯甲酮,3,3’,4,4’-四氨基联苯甲烷和3,3’,4,4’-四氨基联苯二甲基甲烷。
5.如权利要求1的膜,特征在于所用芳香二羧酸为间苯二羧酸、对苯二羧酸、邻苯二羧酸、5-羟基间苯二羧酸、4-羟基间苯二羧酸、2-羟基对苯二羧酸、5-氨基间苯二羧酸、5-N,N-二甲基氨基间苯二羧酸、5-N,N-二乙基氨基间苯二羧酸、2,5-二羟基对苯二羧酸、2,5-二羟基间苯二羧酸、2,3-二羟基间苯二羧酸、2,3-二羟基邻苯二羧酸、2,4-二羟基邻苯二羧酸、3,4-二羟基邻苯二羧酸、3-氟邻苯二羧酸、5-氟间苯二羧酸、2-氟对苯二羧酸、四氟邻苯二羧酸、四氟间苯二羧酸、四氟对苯二羧酸、1,4-萘二羧酸、1,5-萘二羧酸、2,6-萘二羧酸、2,7-萘二羧酸、联苯甲酸、1,8-二羟基萘-3,6-二羧酸、双(4-羧苯基)醚、苯甲酮-4,4’-二羧酸、双(4-羧苯基)砜、联苯-4,4’二羧酸、4-三氟甲基邻苯二羧酸、2,2-双(4-羧苯基)六氟丙烷、4,4’-芪二羧酸、4-羧基肉桂酸或其C1-C20烷基酯或C5-C12芳基酯或它们的酸酐或它们的氯代酰基。
6.如权利要求1的膜,特征在于所用芳香羧酸为三羧酸、四羧酸或其C1-C20烷基酯或C5-C12芳基酯或它们的酸酐或它们的氯代酰基。
7.如权利要求4的膜,特征在于所用芳香羧酸为1,3,5-苯三羧酸(苯均三羧酸)、1,2,4-苯三羧酸(苯偏三羧酸)、(2-羧苯基)亚氨基二乙酸、3,5,3’-联苯三羧酸、3,5,4’-联苯三羧酸和/或2,4,6-吡啶三羧酸。
8.如权利要求7的膜,特征在于所用芳香羧酸为四羧酸,其C1-C20烷基酯或C5-C12芳基酯或它们的酸酐或它们的氯代酰基。
9.如权利要求8的膜,特征在于所用芳香羧酸为苯-1,2,4,5四羧酸、萘-1,4,5,8-四羧酸、3,5,3’,5’-联苯四羧酸、苯甲酮四羧酸、3,3’,4,4’-联苯四羧酸、2,2’,3,3’-联苯四羧酸、1,2,5,6-萘四羧酸及1,4,5,8-萘四羧酸。
10.如权利要求6的膜,特征在于三羧酸或四羧酸的含量基于所用二羧酸为0-30mol%。
11.如权利要求10的膜,特征在于三羧酸或四羧酸的含量基于所用二羧酸为0.1-20mol%。
12.如权利要求10的膜,特征在于三羧酸或四羧酸的含量基于所用二羧酸为0.5-10mol%。
13.如权利要求1的膜,特征在于所用杂芳香羧酸为杂芳香二羧酸和三羟酸和四羧酸,其中在芳香部分有至少一个氮、氧、硫或磷原子,及其C1-C20烷基酯或C5-C12芳基酯或它们的酸酐或它们的氯代酰基。
14.如权利要求13的膜,特征在于所用杂芳香羧酸为吡啶-2,5-二羧酸、吡啶-3,5-二羧酸、吡啶-2,6-二羧酸、吡啶-2,4-二羧酸、4-苯基-2,5-吡啶-二羧酸、3,5-吡唑二羧酸、2,6-嘧啶二羧酸、2,5-吡嗪二羧酸、2,4,6-吡啶三羧酸、苯并咪唑-5,6-二羧酸。
15.如权利要求1的膜,特征在于步骤A)中所用磺化剂选自i)>95%的浓缩硫酸,ii)氯磺酸,iii)SO3与路易斯碱或其它有机组分的复合物;iv)酰基或烷基硫酸盐;v)有机磺酸;或vi)i~v的混合物。
16.如权利要求1的膜,特征在于所用的芳香和杂芳香二氨基羧酸为二氨基苯甲酸及其一氢氯化物和二氢氯化物的衍生物。
17.如权利要求1的膜,特征在于步骤A)中所用多磷酸以P2O5计的分析值,以酸滴定为至少83%。
18.如权利要求1的膜,特征在于步骤C)中形成的聚合物含有通式(I)和/或(II)和/或(III)和/或(IV)和/或(V)和/或(VI)和/或(VII)和/或(VIII)和/或(IX)和/或(X)和/或(XI)和/或(XII)和/或(XIII)和/或(XIV)和/或(XV)和/或(XVI)和/或(XVII)和/或(XVIII)和/或(XIX)和/或(XX)和/或(XXI)和/或(XXII)的重复的吡咯单元,
其中
Ar相同或不同地,各自为四价芳香或杂芳香基团,可为一个或多个环,
Ar1相同或不同地,各自为二价芳香或杂芳香基团,可为一个或多个环,
Ar2相同或不同地,各自为二价或三价芳香或杂芳香基团,可为一个或多个环,
Ar3相同或不同地,各自为三价芳香或杂芳香基团,可为一个或多个环,
Ar4相同或不同地,各自为三价芳香或杂芳香基团,可为一个或多个环,
Ar5相同或不同地,各自为四价芳香或杂芳香基团,可为一个或多个环,
Ar6相同或不同地,各自为二价芳香或杂芳香基团,可为一个或多个环,
Ar7相同或不同地,各自为二价芳香或杂芳香基团,可为一个或多个环,
Ar8相同或不同地,各自为三价芳香或杂芳香基团,可为一个或多个环,
Ar9相同或不同地,各自为二价或三价或四价芳香或杂芳香基团,可为一个或多个环,
Ar10相同或不同地,各自为二价或三价芳香或杂芳香基团,可为一个或多个环,
Ar11相同或不同地,各自为二价芳香或杂芳香基团,可为一个或多个环,
X相同或不同地,各自为氧、硫或含有一个氢原子的氨基,含有1-20个碳原子的基团,或芳基作为另外的基团,
R相同或不同地,各自为氢、烷基或芳基且
n,m各自为大于或等于10的整数,
其中
基团R相同或不同,各自为烷基或芳基,及
n是等于或大于10的整数。
19.如权利要求18的膜,特征在于X为带或不带支链的烷基或烷氧基。
20.如权利要求18的膜,特征在于n,m各自大于或等于100。
21.如权利要求1的膜,特征在于通过在步骤A)之后及步骤B)之前加入磷酸调节粘度。
22.如权利要求1的膜,特征在于在步骤D)中在水汽或水和/或水蒸气存在下,在温度为大于0-150℃下处理膜。
23.如权利要求1的膜,特征在于在步骤D)中在温度为10-120℃下处理膜。
24.如权利要求1的膜,特征在于在步骤D)中在温度为室温(20℃)至90℃下处理膜。
25.如权利要求1的膜,其中在步骤A)中将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体含有至少两个酸基的芳香羧酸或其酯,或一种或多种芳香和/或杂芳香二氨基羧酸,与多磷酸/磺化剂的混合物加热到高到350℃;并部分或全部省去步骤C)。
26.如权利要求1的膜,其中在步骤A)中,将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体含有至少两个酸基的芳香羧酸或其酯,或一种或多种芳香和/或杂芳香二氨基羧酸,与多磷酸的混合物加热到高到350℃;随后用磺化剂对所得到的聚合物多磷酸溶液进行磺化;并部分或全部省去步骤C)。
27.一种电极,具有基于含有重复苯并咪唑单元聚合物的质子导电聚合物涂层,该涂层得自包括如下步骤的方法:
A)将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体含有至少两个羧酸基和至少一个磺酸基的芳香磺羧酸或其酯,或将一种或多种芳香和/或杂芳香磺化二氨基羧酸,混入多磷酸中,形成溶液和/或分散液,
B)将步骤A)得到的混合物涂覆一层至电极上,
C)步骤B)描述的所得片状结构/层在惰性气体及在高达350℃加热以制备聚吡咯聚合物,
D)在水汽存在下在一定温度处理步骤C)中形成的膜足够长时间以使层在用于燃料电池中时具有足够的强度。
28.如权利要求27的电极,特征在于步骤C)中的加热温度为高至280℃。
29.一种膜电极单元,含有至少一个电极,和如权利要求1至26的一个或多个中所述的至少一个膜。
30.一种膜电极单元,含有至少一个如权利要求27或28所述的电极,和如权利要求1至26一个或多个中所述的至少一个膜。
31.一种燃料电池,含有一个或多个如权利要求29或30的膜电极单元。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10228657A DE10228657A1 (de) | 2002-06-27 | 2002-06-27 | Protonenleitende Membran und deren Verwendung |
DE10228657.4 | 2002-06-27 |
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CN1697852A CN1697852A (zh) | 2005-11-16 |
CN1326917C true CN1326917C (zh) | 2007-07-18 |
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CNB038202387A Expired - Fee Related CN1326917C (zh) | 2002-06-27 | 2003-06-14 | 质子导电膜及其应用 |
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US (1) | US8076379B2 (zh) |
EP (1) | EP1519981B1 (zh) |
JP (1) | JP4537199B2 (zh) |
KR (1) | KR20050043802A (zh) |
CN (1) | CN1326917C (zh) |
AT (1) | ATE331753T1 (zh) |
CA (1) | CA2491239A1 (zh) |
DE (2) | DE10228657A1 (zh) |
WO (1) | WO2004003061A1 (zh) |
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EP1483316B1 (de) | 2002-03-06 | 2007-09-19 | Pemeas GmbH | PROTONENLEITENDE ELEKTROLYTMEMBRAN MIT GERINGER METHANOLDURCHLÄSSIGKEIT UND DEREN ANWENDUNG IN BRENNSTOFFZELLEN |
DE10235358A1 (de) * | 2002-08-02 | 2004-02-12 | Celanese Ventures Gmbh | Protonenleitende Polymermembran umfassend Phosphonsäuregruppen enthaltende Polymere und deren Anwendung in Brennstoffzellen |
DE10242708A1 (de) | 2002-09-13 | 2004-05-19 | Celanese Ventures Gmbh | Protonenleitende Membranen und deren Verwendung |
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DE10246372A1 (de) * | 2002-10-04 | 2004-04-15 | Celanese Ventures Gmbh | Mit einer Katalysatorschicht beschichtete protonenleitende Polymermembran enthaltend Polyazole und deren Anwendung in Brennstoffzellen |
EP1652259A2 (de) | 2003-07-27 | 2006-05-03 | Pemeas GmbH | Protonenleitende membran und deren verwendung |
DE102004044760A1 (de) * | 2004-09-16 | 2006-05-24 | Volkswagen Ag | Polymer-Membran, Membran-Elektroden-Einheit mit einer Polymer-Membran, Brennstoffzellenelektrode und Verfahren zur Herstellung |
JP4664641B2 (ja) * | 2004-09-29 | 2011-04-06 | 株式会社東芝 | プロトン伝導膜及び燃料電池 |
DE102005020604A1 (de) * | 2005-05-03 | 2006-11-16 | Pemeas Gmbh | Brennstoffzellen mit geringerem Gewicht und Volumen |
US8557472B2 (en) * | 2005-06-03 | 2013-10-15 | Toyo Boseki Kabushiki Kaisha | Proton conducting polymer membrane, method for production thereof and fuel cell therewith |
DE102005058578A1 (de) * | 2005-12-08 | 2007-06-28 | Sartorius Ag | Membranen aus Polyazolen, Verfahren zu ihrer Herstellung und Brennstoffzellen unter Verwendung derartiger Membranen |
CN100390222C (zh) * | 2006-03-13 | 2008-05-28 | 吉林大学 | 磺化聚合物/聚吡咯复合质子交换膜的制备方法 |
US7989116B2 (en) * | 2007-05-08 | 2011-08-02 | Toyota Motor Engineering & Manufacturing North America, Inc. | Electrolyte utilizing a lewis acid/bronstead acid complex |
CN101302339B (zh) * | 2007-05-09 | 2010-10-27 | 郑州泰达电子材料科技有限公司 | 导电性聚合物组合物和使用该组合物的固体电解电容器 |
EP2240465B1 (en) * | 2008-01-30 | 2015-10-14 | Sikkema, Doetze Jakob | Novel phenol compounds and (co)polymers thereof |
JP4444355B2 (ja) * | 2008-09-03 | 2010-03-31 | 株式会社東芝 | 燃料電池 |
DE102009001141A1 (de) * | 2008-10-29 | 2010-05-06 | Volkswagen Ag | Verfahren zur Herstellung einer Polymerelektrolytmembran |
JP5396902B2 (ja) * | 2009-02-20 | 2014-01-22 | Tdk株式会社 | リチウムイオン二次電池 |
CN104530182A (zh) | 2009-07-27 | 2015-04-22 | 利普森技术有限公司 | 非凝血蛋白的糖基多唾液酸化 |
US9543607B2 (en) | 2013-02-22 | 2017-01-10 | National Research Council Of Canada | Process for producing ion exchange membranes by melt-processing of acidic PFSA ionomers |
KR102273035B1 (ko) | 2014-04-07 | 2021-07-06 | 도레이 카부시키가이샤 | 고분자 전해질 조성물 및 그것을 사용한 고분자 전해질막, 막전극 복합체 및 고체 고분자형 연료 전지 |
RU2563255C1 (ru) * | 2014-09-22 | 2015-09-20 | Федеральное государственное бюджетное учреждение науки Институт неорганической химии им. А.В. Николаева Сибирского отделения Российской академии наук | Композиционный протонпроводящий материал |
CN108841020B (zh) * | 2018-05-16 | 2020-05-19 | 天津理工大学 | 一种具有离子导通性能的微孔聚合物膜及其制备方法及应用 |
CN112838252A (zh) * | 2019-11-25 | 2021-05-25 | 嘉应学院 | 一种燃料电池用高质子电导率的质子交换膜及其制备方法与应用 |
CN114288855B (zh) * | 2021-11-25 | 2023-03-10 | 国家电投集团氢能科技发展有限公司 | 一种水电解膜及其制备方法 |
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-
2002
- 2002-06-27 DE DE10228657A patent/DE10228657A1/de not_active Withdrawn
-
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- 2003-06-14 CN CNB038202387A patent/CN1326917C/zh not_active Expired - Fee Related
- 2003-06-14 US US10/519,281 patent/US8076379B2/en not_active Expired - Fee Related
- 2003-06-14 WO PCT/EP2003/006308 patent/WO2004003061A1/de active IP Right Grant
- 2003-06-14 DE DE50304073T patent/DE50304073D1/de not_active Expired - Lifetime
- 2003-06-14 EP EP03740253A patent/EP1519981B1/de not_active Expired - Lifetime
- 2003-06-14 KR KR1020047021336A patent/KR20050043802A/ko not_active Application Discontinuation
- 2003-06-14 CA CA002491239A patent/CA2491239A1/en not_active Abandoned
- 2003-06-14 JP JP2004516602A patent/JP4537199B2/ja not_active Expired - Fee Related
- 2003-06-14 AT AT03740253T patent/ATE331753T1/de not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
---|---|
CN1697852A (zh) | 2005-11-16 |
EP1519981A1 (de) | 2005-04-06 |
EP1519981B1 (de) | 2006-06-28 |
DE10228657A1 (de) | 2004-01-15 |
WO2004003061A1 (de) | 2004-01-08 |
KR20050043802A (ko) | 2005-05-11 |
CA2491239A1 (en) | 2004-01-08 |
JP4537199B2 (ja) | 2010-09-01 |
DE50304073D1 (de) | 2006-08-10 |
ATE331753T1 (de) | 2006-07-15 |
US8076379B2 (en) | 2011-12-13 |
JP2006507372A (ja) | 2006-03-02 |
US20060057449A1 (en) | 2006-03-16 |
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