WO2003030289A2 - Membrane polymere pour piles a combustible et procede de production de ladite membrane - Google Patents
Membrane polymere pour piles a combustible et procede de production de ladite membrane Download PDFInfo
- Publication number
- WO2003030289A2 WO2003030289A2 PCT/DE2002/003736 DE0203736W WO03030289A2 WO 2003030289 A2 WO2003030289 A2 WO 2003030289A2 DE 0203736 W DE0203736 W DE 0203736W WO 03030289 A2 WO03030289 A2 WO 03030289A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- membrane
- segment
- acid
- ether
- block
- Prior art date
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 229920005597 polymer membrane Polymers 0.000 title abstract 2
- 239000012528 membrane Substances 0.000 claims abstract description 130
- 229920006030 multiblock copolymer Polymers 0.000 claims abstract description 19
- -1 ether sulfone Chemical class 0.000 claims description 67
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 22
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 11
- 150000003457 sulfones Chemical class 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 210000000170 cell membrane Anatomy 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 239000012876 carrier material Substances 0.000 claims description 4
- 239000004753 textile Substances 0.000 claims description 4
- 150000004984 aromatic diamines Chemical class 0.000 claims description 3
- 150000003949 imides Chemical group 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 239000013043 chemical agent Substances 0.000 claims 1
- 238000004132 cross linking Methods 0.000 claims 1
- 230000005855 radiation Effects 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 102
- 230000014759 maintenance of location Effects 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 6
- 229920000359 diblock copolymer Polymers 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 45
- 210000004027 cell Anatomy 0.000 description 19
- 239000000178 monomer Substances 0.000 description 19
- 229920000557 Nafion® Polymers 0.000 description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 229920001400 block copolymer Polymers 0.000 description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 10
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 7
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004696 Poly ether ether ketone Substances 0.000 description 5
- 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 5
- 230000035699 permeability Effects 0.000 description 5
- 229920002530 polyetherether ketone Polymers 0.000 description 5
- YAAWASYJIRZXSZ-UHFFFAOYSA-N pyrimidine-2,4-diamine Chemical compound NC1=CC=NC(N)=N1 YAAWASYJIRZXSZ-UHFFFAOYSA-N 0.000 description 5
- 238000006277 sulfonation reaction Methods 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical group CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 description 4
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 4
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 4
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical group FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 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 description 4
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 4
- KOGDFDWINXIWHI-OWOJBTEDSA-N 4-[(e)-2-(4-aminophenyl)ethenyl]aniline Chemical compound C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1 KOGDFDWINXIWHI-OWOJBTEDSA-N 0.000 description 4
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 4
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 4
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 4
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229940018564 m-phenylenediamine Drugs 0.000 description 4
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 4
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 4
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 4
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 3
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 3
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 description 3
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 description 3
- PKKGGWLTUCMSSD-UHFFFAOYSA-N 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid Chemical compound CC1=C(N)C(C)=C(S(O)(=O)=O)C(C)=C1N PKKGGWLTUCMSSD-UHFFFAOYSA-N 0.000 description 3
- MBJAPGAZEWPEFB-UHFFFAOYSA-N 5-amino-2-(4-amino-2-sulfophenyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1C1=CC=C(N)C=C1S(O)(=O)=O MBJAPGAZEWPEFB-UHFFFAOYSA-N 0.000 description 3
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- MISVBCMQSJUHMH-UHFFFAOYSA-N pyrimidine-4,6-diamine Chemical compound NC1=CC(N)=NC=N1 MISVBCMQSJUHMH-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 2
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 2
- OYPPZOBVPJYLBU-UHFFFAOYSA-N 1-n,4-n,4-n-tris(trimethylsilyl)benzene-1,4-diamine Chemical compound C[Si](C)(C)NC1=CC=C(N([Si](C)(C)C)[Si](C)(C)C)C=C1 OYPPZOBVPJYLBU-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 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 description 2
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 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 description 2
- ALIQZUMMPOYCIS-UHFFFAOYSA-N benzene-1,3-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1 ALIQZUMMPOYCIS-UHFFFAOYSA-N 0.000 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 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006326 desulfonation Effects 0.000 description 2
- 238000005869 desulfonation reaction Methods 0.000 description 2
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 2
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ZYECOKBMCJLBCR-UHFFFAOYSA-N phenazine-1,2,7,8-tetramine Chemical compound C1=C(N)C(N)=CC2=NC3=C(N)C(N)=CC=C3N=C21 ZYECOKBMCJLBCR-UHFFFAOYSA-N 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- SMXXYBNSBNDJGE-UHFFFAOYSA-N (4,4-diaminocyclohexa-1,5-dien-1-yl)-phenylmethanone Chemical compound C1=CC(N)(N)CC=C1C(=O)C1=CC=CC=C1 SMXXYBNSBNDJGE-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- WGGYLJXUYLKOHU-UHFFFAOYSA-N 1,5-diaminocyclohexa-2,4-dien-1-ol Chemical compound NC1=CC=CC(N)(O)C1 WGGYLJXUYLKOHU-UHFFFAOYSA-N 0.000 description 1
- VCHOFVSNWYPAEF-UHFFFAOYSA-N 1-(3-acetylphenyl)ethanone Chemical compound CC(=O)C1=CC=CC(C(C)=O)=C1 VCHOFVSNWYPAEF-UHFFFAOYSA-N 0.000 description 1
- SKBBQSLSGRSQAJ-UHFFFAOYSA-N 1-(4-acetylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)=O)C=C1 SKBBQSLSGRSQAJ-UHFFFAOYSA-N 0.000 description 1
- YSTSBXDVNKYPTR-UHFFFAOYSA-N 1-[4-(4-acetylphenyl)phenyl]ethanone Chemical group C1=CC(C(=O)C)=CC=C1C1=CC=C(C(C)=O)C=C1 YSTSBXDVNKYPTR-UHFFFAOYSA-N 0.000 description 1
- JBDYORUCEWAWQR-UHFFFAOYSA-N 1-[4-(4-acetylphenyl)sulfanylphenyl]ethanone Chemical compound C1=CC(C(=O)C)=CC=C1SC1=CC=C(C(C)=O)C=C1 JBDYORUCEWAWQR-UHFFFAOYSA-N 0.000 description 1
- UTELZOWACOGDKG-UHFFFAOYSA-N 1-[4-[(4-acetylphenyl)methyl]phenyl]ethanone Chemical compound C1=CC(C(=O)C)=CC=C1CC1=CC=C(C(C)=O)C=C1 UTELZOWACOGDKG-UHFFFAOYSA-N 0.000 description 1
- QBKJESDEARMHGB-UHFFFAOYSA-N 2,5-dihydroxybenzene-1,3-disulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=C(O)C(S(O)(=O)=O)=C1 QBKJESDEARMHGB-UHFFFAOYSA-N 0.000 description 1
- VSAZFRKEFQPOIS-UHFFFAOYSA-N 2,5-dihydroxybenzene-1,4-disulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=C(O)C=C1S(O)(=O)=O VSAZFRKEFQPOIS-UHFFFAOYSA-N 0.000 description 1
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DWUUPAUTLKFPLO-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-dithiol Chemical compound NC1=CC(N)=C(S)C=C1S DWUUPAUTLKFPLO-UHFFFAOYSA-N 0.000 description 1
- MTNLEKFLKGGTKS-UHFFFAOYSA-N 4-(2,4-diaminophenoxy)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC=C1OC1=CC=C(N)C=C1N MTNLEKFLKGGTKS-UHFFFAOYSA-N 0.000 description 1
- RQBIGPMJQUKYAH-UHFFFAOYSA-N 4-(3,4-diaminophenoxy)benzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1OC1=CC=C(N)C(N)=C1 RQBIGPMJQUKYAH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- 229920003934 Aciplex® Polymers 0.000 description 1
- XKSZKZLQNSTNJC-UHFFFAOYSA-N C[Si](C)(C)C=1C(=C(O)C=CC=1C(C)(C)C1=CC=C(C=C1)O)[Si](C)(C)C Chemical compound C[Si](C)(C)C=1C(=C(O)C=CC=1C(C)(C)C1=CC=C(C=C1)O)[Si](C)(C)C XKSZKZLQNSTNJC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000005362 aryl sulfone group Chemical group 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- WRUAHXANJKHFIL-UHFFFAOYSA-N benzene-1,3-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(S(O)(=O)=O)=C1 WRUAHXANJKHFIL-UHFFFAOYSA-N 0.000 description 1
- OATNQHYJXLHTEW-UHFFFAOYSA-N benzene-1,4-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(S(O)(=O)=O)C=C1 OATNQHYJXLHTEW-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- CTIKAHQFRQTTAY-UHFFFAOYSA-N fluoro(trimethyl)silane Chemical compound C[Si](C)(C)F CTIKAHQFRQTTAY-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- FITZJYAVATZPMJ-UHFFFAOYSA-N naphthalene-2,6-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(S(=O)(=O)O)=CC=C21 FITZJYAVATZPMJ-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 229920006120 non-fluorinated polymer Polymers 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229920003936 perfluorinated ionomer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920003208 poly(ethylene sulfide) Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- ABYXFACYSGVHCW-UHFFFAOYSA-N pyridine-3,5-diamine Chemical compound NC1=CN=CC(N)=C1 ABYXFACYSGVHCW-UHFFFAOYSA-N 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- 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
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- 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
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
-
- 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
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
- C08J2365/02—Polyphenylenes
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates to the fields of power generation, vehicle construction and chemistry and relates to polymer fuel cell membranes, such as those that can be used, for example, in direct methanol fuel cells, and a method for their production.
- B. the hydrogen-powered fuel cells or the direct methanol fuel cells comes to the polymer electrolyte membranes (PEM).
- PEM polymer electrolyte membranes
- the task is, on the one hand, to separate the two electrode compartments from each other and to minimize the methanol permeability, and on the other hand, the proton transport between the anode compartment (in which the hydrogen is oxidized to protons or methanol to protons and carbon dioxide) and the cathode compartment (in which oxygen is reduced) to ensure.
- the minimization of the methanol permeability is necessary because the reaction of methanol with oxygen in the cathode compartment leads to a reduction in performance.
- the requirements for the PEM for use in fuel cells are as follows: 1. high chemical and electrochemical stability, especially under operating conditions 2. high mechanical stability during operation
- cation exchange membranes based on perfluorinated hydrocarbons, which were initially developed for chlor-alkali electrolysis, have been used in fuel cells. Proton conductivity is achieved through sulfonic acid groups in the side chains of these polymers.
- Such membranes are known under the trade names Nafion® (DuPont), Dow ⁇ Membran (Dow Chemical), Flemion® (Asahi Glass Co., Ltd) and Aciplex® (Asahi Chemical Industry Co., Ltd).
- a big disadvantage of these membranes is their high price (approx. US $ 800 / m 2 ).
- Another disadvantage is their methanol permeability, especially at higher methanol concentrations, so that the fuel cells cannot be operated under optimal conditions.
- these membranes dry out at operating temperatures> 100 ° C, which leads to a reduction in proton conductivity. Nevertheless, these temperatures are e.g.
- Reinforced membranes based on PTFE microfiltration membranes coated with a perfluorinated ionomer are also known (GoreSelect TM, Gore and Associates; US 5,547,551). This technique allows the production of thinner membranes, leading to a reduction of the ohmic resistance.
- the proton conductivity is lower than that of the Nafion ® or Dow ® membranes mentioned above.
- Membrane materials in fuel cells have been developed e.g. B. described by Ballard (US 5,422,411). Compared to the analog, non-fluorinated polymers, these materials have a significantly higher oxidation stability. In hydrogen fuel cells, these membranes have better electrical properties than Nafion ® or Dow ® membranes.
- Polybenzimidazole membranes have been described (B. Cahan, JS Wainright, J. Electrochem. Soc. 140, L185 (1994); P. Staiti, M. Minutoli, S. Hocevar, J. Power Sources 90, 231 - 235 (2000) ). These membranes have to be impregnated with phosphoric acid, poly-tungstic acid or phosphorotungstic acid in order to achieve proton conductivity. The acid is bound to the matrix with salt formation with the imidazole groups of the polymer. The ratio of imidazole to acid is of the order of 1: 3 to 1: 5. With these materials, however, there is a risk that the acid will be carried out of the membrane by the water formed during operation and thus the proton conductivity will be lost.
- PES polyaryl ether sulfone
- PEM polyaryl ether sulfone
- Degrees of sulfonation above 29.5% lead to water-soluble products.
- Degrees of sulfonation of up to 29% give products that are soluble in hot water.
- these materials swell very much, which leads to poor mechanical properties.
- Crosslinked sulfonated polyether sulfones have a lower swellability, but the specific conductivity decreases by a factor of 2 compared to the uncrosslinked products.
- EP 0 574 791 A2 describes sulfonated polyether ether ketone (PEEK) as membrane material for use in fuel cells.
- PEEK polyether ether ketone
- high degrees of sulfonation which are necessary for sufficient proton conductivity, lead to materials with high degrees of swelling and thus poor mechanical properties (shortening the life of the membrane).
- inhomogeneously sulfonated PEEK there is a risk of embrittlement due to recrystallization, since PEEK itself is partially crystalline.
- a major disadvantage of all previously known polymeric membranes for fuel cells is the insufficient mechanical stability and / or the insufficient methanol retention capacity.
- the object of the present invention is to provide a polymer fuel cell membrane which has improved mechanical stability and / or a substantially improved methanol retention capacity.
- the present invention provides polymer fuel cell membranes that can overcome existing deficiencies in the prior art.
- the polymeric fuel cell membranes according to the invention can consist of one or more separation-active layers. It is also possible for one or more carriers to be present. Materials are used as supports which at least do not completely prevent or prevent the function of the release-active layer (s), advantageously they support the function of the release-active layer (s). One or more release-active layer (s) can be applied to a support, the release-active layer (s) can be arranged between two supports, the material of the release-active layer (s) can also be applied, for example, in cavities, pores of a support material , Combinations of these options can also be implemented.
- the carrier should primarily ensure and / or increase the mechanical stability of the membrane. It is advantageously constructed from a textile or porous material.
- the release-active layer according to the invention consists of at least one di- and / or multiblock copolymer with one of the general segment structures A- (B- A) k and / or B- (AB) ⁇ and / or (AB) m with k> 1 and I> 1 and m> 1.
- these segment structures can also be present side by side and in different numbers.
- the di- and / or multiblock copolymers can be linear or branched.
- the block segments (A) and (B) each consist of oligomer segments, the block segment (A) consisting of at least one Electron-non-conductive and proton-non-conductive oligomer segment, and the block segment (B) is composed of at least one proton-conductive and electron-non-conductive oligomer segment.
- oligomers are compounds which consist of a small number of monomeric molecules. They are called dimers, trimers, tetramers, etc. (Stoeckhert, Kunststofflexikon 9th edition, Carl Hanser Verlag Ober Wien 1998).
- the oligomers advantageously have degrees of polymerization of 2 to 50.
- the oligomers present, both from block segment (A) and from block segment (B), can each consist of the same or different oligomer units, with (A) and (B) not having the same oligomer units.
- the length of the block segment (B) in particular should advantageously be selected according to an optimal proton conductivity.
- the membrane according to the invention must have a morphologically structure with an essentially continuous proton conductivity. This means that the structure of the membrane with regard to the arrangement of supports and separation-active layers must be selected according to this criterion. Of course, the highest possible proton conductivity is sought. It is advantageous if the separation-active layer is structured in essentially unmixed proton-conducting and non-conducting polymer regions.
- compositions in which the block segments (A) and (B) have imide structures and the block segment (B) have sulfonic acid groups bonded directly to an aromatic diamine component of the aromatic imide structure are excluded from the composition of the membrane according to the invention. Also excluded from the composition according to the invention are compositions in which the block segment (B) contains sulfonic acid groups which are bonded directly to the aromatics and which, under the respective operating or. Desulfonate operating conditions. This desulfonation occurs particularly in the case of deactivated aromatics, ie aromatics with strongly electron-withdrawing substituents / groups.
- polyether sulfones bearing sulfonic acid groups in which the sulfonic acid group is present directly bound to the aryl sulfone component (aromatics coupled via sulfone group), relatively easily in the aqueous system or under operating or operating conditions in a fuel cell.
- no desulfonation of the sulfonic acid groups which are directly coupled to the ether building block has been found.
- the oligomeric block segments (A) comprise at least one oligomer of the compound classes Oligoarylimid and / or Oligoarylensulfid and / or Oligoarylsulfon and / or Oligoarylethersulfon and / or Oligoarylenether and / or Oligoaryletherketon and / or Oligoarylenetheretherketon and / or synthesized oligoaramide and / or Oligoarylharnstoff and / or Oligoarylenoxadiazole and / or oligoarylenesulfonamide and / or oligobenzimidazole and / or oligobenzoxazole and / or oligobenzothiazole and / or oligoquinoxaline.
- the degree of polymerization of the block segments (A) is in the range from 1 to 50, advantageously in the range from 4 to 30 and still advantageously between 5 and 10.
- the block segment (B) advantageously consists of at least one oligomer segment of the compound classes oligoarylene sulfide and / or oligoaryl sulfone and / or oligoaryl ether sulfone and / or oligoarylene ether and / or oligoaryl ether ketone and / or oligoarylene ether ether ketone and / or oligoaramide and / or oligoaryol urea and / or oladialol or urea and / or oxadiall urea and / or Oligoarylenesulfonamide and / or oligobenzimidazole and / or oligobenzoxazole and / or oligobenzthiazole and / or oligoquinoxaline and / or oligoarylimide, with the exception of this oligoarylimide a sulfonic acid group B directly attached to an aromatic amine component of an aromatic
- the block segment (B) consists of at least one oligomer segment of the compound classes oligoarylene sulfide and / or oligoaryl sulfone and / or oligoaryl ether sulfone and / or oligoarylene ether and / or oligoaryl ether ketone and / or oligoarylene ether ether ketone and / or oligoaryl amide and / or oligoaryl urea and / or oligoarylenoxadiazole and / or oligoarylene sulfonamide and / or oligobobolizole / and / or oligobobolizole / and / or oligobenzolid / and / or oligobenzolid / and / or oligobenzolid / and / or oligobenzolid / and / or oligobenzolid / and / or oligobenzolid / and /
- the block segment (B) can advantageously also be composed of at least one oligomer segment of the compound classes oligoarylene sulfide and / or oligoaryl sulfone and / or oligoaryl ether sulfone and / or oligoarylene ether and / or oligoaryl ether ketone and / or oligoarylene ether ether ketone and / or oligoaramide and / or oligoaryol urea and / or oladialol or urea and / or oladialol or urea and / or oladialol or urea and / or oladialol or urethane and / or Oligoarylenesulfonamide and / or oligobenzimidazole and / or oligobenzoxazole and / or oligobenzthiazole and / or oligoarylimide and / or oligoquinoxaline
- the membrane in the separating layer can advantageously contain further polymers and / or further additives.
- the block segment (A) acts primarily Improve mechanical stability and methanol retention.
- the block segment (B) is itself proton-conductive and retains the methanol with high selectivity.
- Such a membrane is advantageously composed of a block segment (A) made from oligoimide (s) and / or oligophenylene sulfide (s) and / or oligosulfonamide (s) and / or oligoarylsulfone (s) and / or oligobenzimidazole (s) and from a block segment (B ) built up from oligophenylene sulfide (s) and / or oligosulfonamide (s) and / or oligoarylsulfone (s) and / or oligobenzimidazole (s) and / or oligoimide (s) with the proton-conducting sulfonic acid and / or phosphonic acid groups, with the exception of the block segments (A) and (B) have an imide structure and the block segment (B) has a sulfonic acid group bonded directly to an aromatic diamine building block of the aromatic imide structure, and has
- starting materials are used which lead to block segments (A) with at least one electron-non-conductive and proton-non-conductive oligomer segment and which lead to block segments (B ) lead with at least one proton-conducting and electron-non-conducting oligomer segment.
- At least one of the starting materials for the production of the block segment (A) and / or (B) is present as a solution or as a melt.
- the oligomeric block segments (A) and (B), each with different reactive end groups, which are necessary for coupling the block segments (A) with the block segments (B), are first prepared in separate reactions. Both the block length and the type of reactive end groups are determined by the composition of the starting materials.
- the chain lengths of the block segments and the reactive functional end groups are adjusted by a defined excess of one of the monomers of the type CC or DD, as shown schematically in Formula 1.
- a check is made to control the chain length and the reactive functional end groups difunctional monomer of type CC and / or DD added in a defined ratio to component CD to the reaction mixture (see formula 2).
- block segments according to the invention Another property of the block segments according to the invention is that the functionalities of their end groups only allow the block segments (A) and (B) to be coupled.
- the block segments (B) are obtained by reacting monomers, the sulfonic acid (s) and / or phosphonic acid (s) and / or (perfluoro) alkylsulfonic acid (s) and / or (perfluoro) alkylphosphonic acid (s) and / or (perfluoro ) Alkyl carboxylic acid (s) and / or of monomers which contain at least one further proton non-conductive functional group such as.
- B. contain hydroxyl groups, which is not involved in the chain structure and which can be converted into a proton-conducting group by polymer-analogous reactions of the block segments.
- a criterion for the selection of the monomers to be used to produce a block segment (B) is the density of the proton-conducting groups DPIG, defined by:
- the density Dp ⁇ G should advantageously be adjusted by adding monomers without proton-conducting groups in the range from 20% to 200%.
- the group density is advantageously between 50 and 100%.
- the degree of polymerization of the proton-conducting block segments (B) is in the range from 1 to 50, advantageously in the range from 1 to 30 and even more advantageously between 2 and 10.
- ⁇ -propane sultone, ⁇ -butane sultone, or 1, 2,2-trifluoro-2-hydroxy-1-trifluoromethylethane sultone (perfluoro) alkyl lactones can be obtained from the corresponding oligomeric block segments of type (A). This method is particularly advantageous if the oligomer synthesis must be carried out in melt but also in solution at temperatures above 200 ° C.
- the multiblock copolymers of the general form A- (BA) ⁇ are advantageously obtained, k advantageously Can take values between 2 and 10.
- This structure enables the finished membrane to have a largely phase-separated morphology with block segment (A) -rich phases (A-phase) and block segment (B) -rich phases (B-phase) and with essentially continuous proton conductivity.
- Proton-non-conductive A phases of this type do not swell or only swell to a small extent in water or water / methanol mixtures and essentially give the membranes mechanical stability. Furthermore, they form a barrier for water and when using the membranes in DMFC for methanol between the anode and cathode compartments of a fuel cell unit.
- Proton conduction between the anode and the cathode takes place via swellable B phases of the membrane materials.
- the lower mechanical stability due to swelling is compensated for by the A phases.
- the B phases in operation in a DMFC form a barrier essentially for methanol between the anode and cathode spaces of a fuel cell unit.
- auxiliaries and additives and / or crosslinking agents can then be added.
- the swellability of the B phase can be controlled during or after membrane production by adding crosslinking agents.
- they are formed as a separation-active layer (s) alone or on and / or between and / or in a support as a membrane, the membrane having a structure with an essentially continuous structure Has proton conductivity.
- Advantageous monomers for the production of oligomeric block segments (A) can be:
- Terephthalic acid isophthalic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5- dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-4,4 '-dicarboxylic acid,
- Diaminopyridine 3.5 diaminopyridine, piperazine, 2,4-diamino-pyrimidine, 4,6-
- Terephthalic acid isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenyl ether-4, 4 '-dicarboxylic acid, cyclohexane-1, 4-dicarboxylic acid, pyridine-dicarboxylic acid 2,6-, 5-hydroxyisophthalic acid and
- Terephthalic acid isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid,
- Terephthalic acid isophthalic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5- dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, biphenyl-4,4 '-dicarboxylic acid, diphenyl ether-4, 4'-dicarboxylic acid, cyclohexane-1, 4-dicarboxylic acid, pyridine 2,6-dicarboxylic acid, 5-hydroxyisophthalic acid and
- Advantageous monomers which only lead to the production of the oligomeric block segments (B), in addition to those mentioned for the production of the block segments (A), can be:
- 5-lsophthalphosphonklare 5-lsophthalsulfonkladish, Terephthalsulfonklad, p-phenylenediaminesulfonic acid, m-phenylenediaminesulfonic acid, 4,4 '-Diaminobiphenyl- 2,2' disulfonic acid, 4,4 'diaminostilbene-2,2' disulfonic acid, 2,4-diaminomesitylene -6- sulfonic acid, 3,5-diaminobenzoic acid 4.
- Combinations of the monomers within a block segment (A) and / or (B) are possible.
- the criterion for the selection of the monomers and their combinations are the properties of the block segments (A) and (B) according to claim 1.
- the carboxylic acid and sulfonic acid-containing monomers are advantageously used as acid chlorides for the synthesis of the oligomeric block segments (A) and (B).
- the carboxylic acid-containing monomers can also be used as methyl or phenyl esters. It is also advantageous to silylate the amino, thiol and hydroxy groups which are involved in the formation of the oligomer. Monomers containing hydroxyl groups can be used in the form of their acetates.
- the conversion of the monomers to the oligomeric block segments (A) and (B) and the preparation of the di- and / or multi-block copolymers takes place in solution or in the melt, at least one of the monomers used being in solution or in the melt.
- Polar aprotic solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), 1,4-dioxane or N-methylpyrrolidone (NMP) are used in particular for the reactions which are carried out in solution , If necessary, up to 5% by mass of low molecular weight salts, such as lithium chloride or calcium chloride, are added to these solvents in order to increase the solubility of the oligomers in the corresponding solvents.
- low molecular weight salts such as lithium chloride or calcium chloride
- the ratio solvent / monomers is chosen so that the oligomer and later the di- and / or multi-block copolymer concentration is in the range between 5 and 30 mass%, preferably between 10 and 20 mass%.
- these solutions are used to produce the membranes.
- the di- and / or multi-block copolymer concentration of these solutions is adjusted so that the solutions have a viscosity which is advantageous for the manufacture of the membranes.
- the viscosity can also be adjusted by partially evaporating the solvent in vacuo or by adding solvent.
- solutions which contain at least one of the di- or multiblock copolymers according to the invention or solutions which contain at least one oligomeric block segment (A) and at least one oligomeric block segment (B) or solutions, which contain at least one oligomeric block segment (A) and / or at least one oligomeric block segment (B) and at least one di- or multiblock copolymer using a doctor blade to form a film with a thickness of 100-500 ⁇ m on an inert, smooth base e.g. B. made of glass, PTFE or stainless steel.
- the oligomeric block segments (A) and (B) are coupled. and / or the or the di- or multiblock copolymers to di- and / or multiblock copolymers instead.
- the solvent is either partially evaporated by supplying energy in air and then completely in a vacuum or immediately completely in a vacuum. The temperatures for this are in the range of 50 - 150 ° C.
- the dry membranes obtained in this way have thicknesses of 50 to 150 ⁇ m, preferably between 60 and 100 ⁇ m, the thickness of the membranes being dependent on the thickness of the polymer film pulled out and the polymer concentration.
- the membranes have a phase-separated morphology with essentially continuous proton conductivity.
- the support material which consists of a porous or textile material, for example polyphenylene oxide or polyphenylene sulfide
- an inert, smooth base e.g. B. made of glass, PTFE or stainless steel or fixed.
- the application of the release-active layer is carried out as described under 1.
- the separation-active layer on the carrier has a phase-separated morphology with essentially continuous proton conductivity.
- the support material which consists of a porous or textile material, for example polyphenylene oxide or polyphenylene sulfide, is impregnated with a solution containing the di- and / or multiblock copolymer.
- the membrane is obtained by evaporating the solvent as described under 1.
- the separation-active layer which is located in the cavities of the carrier, has a phase-separated morphology with essentially continuous proton conductivity.
- a polymer film is first applied to a carrier material as described under 2. Before the solvent is evaporated, a second carrier material is applied to this polymer film. This membrane is finished by evaporating off the solvent, as described under 1.
- the separation-active layer between the supports has a phase-separated morphology with essentially continuous proton conductivity.
- a membrane which has been produced according to one of the options 1 to 4 is coated with a further polymer solution which may contain the same or a different di- and / or multiblock copolymer.
- the membrane is finished by evaporating the solvent as described in 1.
- the additional separation-active layer (s) on the support has a phase-separated morphology with essentially continuous proton conductivity.
- a Nafion membrane (DuPont) is used as the standard membrane for DMFC. This membrane swells in methanol-water solutions (5% by mass of methanol) and the membrane properties are established. Sufficient conductivity is achieved with a proton conductivity of 0.2 S / cm at 80 ° C. The barrier properties of Nafion membranes with a methanol permeability of 30% and more are not suitable for use in DMFC.
- % LiCI contains, at -18 ° C to 0.1 mol of tris-trimethylsilyl-p-phenylenediaminesulfonic acid 0.08 mol of isophthalic acid dichloride are added and the mixture is reacted for one hour at -18 ° C. and 8 hours at 100 ° C. with stirring.
- - Reaction solution B1 (amine-terminated).
- reaction solution B1 is slowly added dropwise to the reaction solution A1 with stirring. After stirring for 1 hour at 120 ° C., 0.05 mol of acetic anhydride are added dropwise and stirring is continued for 1 hour.
- the solution is concentrated under vacuum and stirring and drawn into a membrane and slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained. Methanol retention: 1/20 of the Nafion comparison membrane
- Block copolymer membrane 2 is a block copolymer membrane
- reaction solution B1 is slowly added dropwise to the reaction solution A2 with stirring. After stirring for 1 hour at 120 ° C under vacuum and stirring
- reaction solution B1 is slowly added dropwise to the reaction solution A3 with stirring. After stirring for 1 hour at 130 ° C under vacuum and stirring
- Block copolymer membrane 4
- reaction solution B2 is slowly added dropwise to the reaction solution A1 with stirring. After stirring at 130 ° C. for 8 hours, the solution is concentrated under vacuum and stirring in such a way that the solution is introduced into a fine glass fiber fabric and is slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained. Methanol retention: 3/100 of the Nafion comparison membrane
- Block copolymer membrane 5
- reaction solution B3 is slowly added dropwise to the reaction solution A4 with stirring. After stirring for 8 hours at 130 ° C under vacuum and stirring
- Block copolymer membrane 6
- reaction solution A5 is added to reaction solution B3 with stirring. After stirring at 130 ° C. for 8 hours, the solution is cooled and 0.01 mol of dianediglycidyl ether is added as a crosslinking agent. The solution is immediately drawn out to the membrane, dried under vacuum and annealed at 100 ° C. for 5 hours. An easily manageable, mechanically stable membrane is obtained.
- reaction solution A5 is added to reaction solution B3 with stirring. After stirring at 130 ° C. for 8 hours, the solution is cooled and 0.01 mol of 4,4'-difluorodiphenyl sulfone is added as crosslinking agent. The solution is drawn out to the membrane, dried under vacuum and annealed at 120 ° C. for 8 hours. An easily manageable, mechanically stable membrane is obtained. Methanol retention: 5/100 of the Nafion comparison membrane
- Block copolymer membrane 8
- reaction solution B3 100 ml of reaction solution B3 are slowly added dropwise to 50 ml of reaction solution A2 and 50 ml of reaction solution A4 while stirring. After stirring at 130 ° C. for 8 hours, the solution is concentrated under vacuum and stirring and drawn out to a membrane and slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained.
- Block copolymer membrane 9 is a block copolymer membrane
- reaction solution B1 and 50 ml of reaction solution B3 are slowly added dropwise to 100 ml of reaction solution A1 with stirring. After stirring at 130 ° C. for 8 hours, the solution is concentrated under vacuum and stirring and drawn out to a membrane and slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained. Methanol retention: 4/100 of the Nafion comparison membrane
- Block copolymer membrane 10 is a block copolymer membrane
- reaction solution B1 and 45 ml of reaction solution B3 are slowly added dropwise to 100 ml of reaction solution A1 with stirring. After stirring at 130 ° C. for 8 hours, the solution is concentrated under vacuum and stirring and drawn out to a membrane and slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained.
- reaction solution B2 and 50 ml of reaction solution B3 are slowly added dropwise to 90 ml of reaction solution A1 with stirring. After stirring at 130 ° C. for 8 hours, the solution is concentrated under vacuum and stirring and drawn out to a membrane and slowly dried under vacuum. An easily manageable, mechanically stable membrane is obtained. Methanol retention: 7/100 of the Nafion comparison membrane
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fuel Cell (AREA)
Abstract
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02776768A EP1430560A2 (fr) | 2001-09-28 | 2002-09-27 | Membrane polymere pour piles a combustible et procede de production de ladite membrane |
AU2002339343A AU2002339343A1 (en) | 2001-09-28 | 2002-09-27 | Polymer membrane for fuel cells and method for the production thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10149716.4 | 2001-09-28 | ||
DE10149716A DE10149716A1 (de) | 2001-09-28 | 2001-09-28 | Polymere Brennstoffzellen-Membran und Verfahren zu ihrer Herstellung |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2003030289A2 true WO2003030289A2 (fr) | 2003-04-10 |
WO2003030289A3 WO2003030289A3 (fr) | 2003-11-13 |
Family
ID=7701871
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2002/003736 WO2003030289A2 (fr) | 2001-09-28 | 2002-09-27 | Membrane polymere pour piles a combustible et procede de production de ladite membrane |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1430560A2 (fr) |
AU (1) | AU2002339343A1 (fr) |
DE (1) | DE10149716A1 (fr) |
WO (1) | WO2003030289A2 (fr) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10316323A1 (de) * | 2003-04-10 | 2004-10-28 | Daimlerchrysler Ag | Verfahren zur Herstellung eines basisch funktionalisierten Polyarylethersulfons |
WO2005090439A3 (fr) * | 2004-03-12 | 2005-11-24 | Polyfuel Inc | Copolymeres conducteurs d'ions contenant un ou plusieurs oligomeres conducteurs d'ions |
DE102004055129A1 (de) * | 2004-11-16 | 2006-05-18 | Volkswagen Ag | Polymer-Elektrolyt-Membran für eine Brennstoffzelle sowie Verfahren zu deren Herstellung |
WO2008012222A3 (fr) * | 2006-07-28 | 2008-04-24 | Leibniz Inst Polymerforschung | Composés de polyarylène sulfonés, matériau pour membrane obtenu à partir de ces derniers, procédé de production et d'utilisation desdits composés |
US7459505B2 (en) | 2005-05-03 | 2008-12-02 | General Motors Corporation | Block copolymers with acidic groups |
US7507771B2 (en) | 2003-11-13 | 2009-03-24 | Polyfuel, Inc. | Ion conductive copolymers containing one or more hydrophobic oligomers |
WO2009075974A1 (fr) * | 2007-12-11 | 2009-06-18 | Bose Corporation | Membrane électrolyte polymère de pile à combustible |
US7572535B2 (en) | 2002-05-13 | 2009-08-11 | Polyfuel, Inc. | Ion conductive copolymers containing one or more hydrophobic oligomers |
US7977394B2 (en) | 2005-05-03 | 2011-07-12 | GM Global Technology Operations LLC | Triblock copolymers with acidic groups |
US7993792B2 (en) | 2006-07-26 | 2011-08-09 | GM Global Technology Operations LLC | Polymer blocks for PEM applications |
US8216740B2 (en) | 2006-12-12 | 2012-07-10 | Bose Corporation | Fuel cell |
CN102643546A (zh) * | 2012-05-03 | 2012-08-22 | 长春工业大学 | 含1,3,4-噁二唑环的聚芳醚砜中高温质子交换膜及其制备方法 |
US8492460B2 (en) | 2006-07-28 | 2013-07-23 | GM Global Technology Operations LLC | Fluorinated polymer blocks for PEM applications |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4944880A (en) * | 1989-10-16 | 1990-07-31 | Exxon Research And Engineering Company | Polyimide/aliphatic polyester copolymers |
US5028685A (en) * | 1989-10-16 | 1991-07-02 | Exxon Research & Engineering Company | Halogenated polyurethanes |
SG73410A1 (en) * | 1992-06-13 | 2000-06-20 | Hoechst Ag | Polymer electrolyte membrane and process for the production thereof |
-
2001
- 2001-09-28 DE DE10149716A patent/DE10149716A1/de not_active Withdrawn
-
2002
- 2002-09-27 WO PCT/DE2002/003736 patent/WO2003030289A2/fr not_active Application Discontinuation
- 2002-09-27 EP EP02776768A patent/EP1430560A2/fr not_active Withdrawn
- 2002-09-27 AU AU2002339343A patent/AU2002339343A1/en not_active Abandoned
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7572535B2 (en) | 2002-05-13 | 2009-08-11 | Polyfuel, Inc. | Ion conductive copolymers containing one or more hydrophobic oligomers |
DE10316323A1 (de) * | 2003-04-10 | 2004-10-28 | Daimlerchrysler Ag | Verfahren zur Herstellung eines basisch funktionalisierten Polyarylethersulfons |
US7507771B2 (en) | 2003-11-13 | 2009-03-24 | Polyfuel, Inc. | Ion conductive copolymers containing one or more hydrophobic oligomers |
WO2005090439A3 (fr) * | 2004-03-12 | 2005-11-24 | Polyfuel Inc | Copolymeres conducteurs d'ions contenant un ou plusieurs oligomeres conducteurs d'ions |
JP2007528930A (ja) * | 2004-03-12 | 2007-10-18 | ポリフューエル・インコーポレイテッド | 1種若しくは複数種のイオン伝導性オリゴマーを含有するイオン伝導性コポリマー |
US7504461B2 (en) | 2004-03-12 | 2009-03-17 | Polyfuel, Inc. | Ion-conductive copolymers containing one or more ion-conducting oligomers |
DE102004055129A1 (de) * | 2004-11-16 | 2006-05-18 | Volkswagen Ag | Polymer-Elektrolyt-Membran für eine Brennstoffzelle sowie Verfahren zu deren Herstellung |
US8263672B2 (en) | 2005-05-03 | 2012-09-11 | GM Global Technology Operations LLC | Triblock copolymers with acidic groups |
US7459505B2 (en) | 2005-05-03 | 2008-12-02 | General Motors Corporation | Block copolymers with acidic groups |
US7977394B2 (en) | 2005-05-03 | 2011-07-12 | GM Global Technology Operations LLC | Triblock copolymers with acidic groups |
US7993792B2 (en) | 2006-07-26 | 2011-08-09 | GM Global Technology Operations LLC | Polymer blocks for PEM applications |
US8163864B2 (en) | 2006-07-28 | 2012-04-24 | Leibniz-Institut Fuer Polymerforschung Dresden E.V. | Sulfonated polyarylene compounds, membrane material made therefrom, method for the production thereof and use |
WO2008012222A3 (fr) * | 2006-07-28 | 2008-04-24 | Leibniz Inst Polymerforschung | Composés de polyarylène sulfonés, matériau pour membrane obtenu à partir de ces derniers, procédé de production et d'utilisation desdits composés |
US8492460B2 (en) | 2006-07-28 | 2013-07-23 | GM Global Technology Operations LLC | Fluorinated polymer blocks for PEM applications |
US8216740B2 (en) | 2006-12-12 | 2012-07-10 | Bose Corporation | Fuel cell |
WO2009075974A1 (fr) * | 2007-12-11 | 2009-06-18 | Bose Corporation | Membrane électrolyte polymère de pile à combustible |
US8557473B2 (en) | 2007-12-11 | 2013-10-15 | Bose Corporation | Fuel cell polymer electrolyte membrane |
CN102643546A (zh) * | 2012-05-03 | 2012-08-22 | 长春工业大学 | 含1,3,4-噁二唑环的聚芳醚砜中高温质子交换膜及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE10149716A1 (de) | 2003-04-30 |
EP1430560A2 (fr) | 2004-06-23 |
WO2003030289A3 (fr) | 2003-11-13 |
AU2002339343A1 (en) | 2003-04-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE60214166T2 (de) | Polymerelektrolyt für eine brennstoffzelle des festpolymertyps und brennstoffzelle | |
DE10201886B4 (de) | Polymerelektrolytmembran sowie Verfahren zur Herstellung dieser und Festpolymerelektrolytbrennstoffzelle, welche diese verwendet | |
EP2443172B1 (fr) | Copolymères blocs de polyéthersulfone aromatique | |
EP1971635B1 (fr) | Membrane polymerique conductrice de protons | |
EP1073690B1 (fr) | Melanges constitues d'acides, de bases et de polymeres, et leur utilisation dans des procedes a membrane | |
DE10117686A1 (de) | Protonenleitende Membran und deren Verwendung | |
DE10117687A1 (de) | Protonenleitende Membran und deren Verwendung | |
EP2009728B1 (fr) | Procédé de fabrication d'un polymère poly(1,3,4-oxadiazol) sulfoné | |
EP1901378A1 (fr) | Membrane en polymere conducteur de protons, son procede de production et pile a combustible l'utilisant | |
DE10144815A1 (de) | Protonenleitende Membran und deren Verwendung | |
EP1559164A2 (fr) | Membrane polymere conductrice de protons contenant des melanges de polyazoles, et son utilisation dans des piles a combustible | |
EP1550174A2 (fr) | Membrane conductrice de protons et son utilisation | |
DE10220817A1 (de) | Verfahren zur Herstellung einer gepfropften Polymerelektrolytmembran und deren Anwendung in Brennstoffzellen | |
WO2003030289A2 (fr) | Membrane polymere pour piles a combustible et procede de production de ladite membrane | |
WO2009066952A1 (fr) | Monomère pour polymère conducteur de protons qui comporte un groupe acide dans une chaîne latérale, polymère conducteur de protons obtenu au moyen du monomère, procédé d'obtention du polymère conducteur de protons, membrane électrolytique comportant le polymère conducteur de protons, et ensemble membrane/électrode incluant l'électrolyte | |
JPWO2019188572A1 (ja) | 電解質膜 | |
DE60304541T2 (de) | Elektrodenanordnung für Polymerelektrolytbrennstoffzelle, und diese verwendende Brennstoffzelle | |
DE10155543C2 (de) | Protonenleitende Elektrolytmembran, Verfahren zu ihrer Herstellung und deren Verwendung | |
DE19909028A1 (de) | Sulfonierte aromatische Polymere, Membran enthaltend diese Polymeren, Verfahren zu deren Herstellung und deren Verwendung | |
EP1420039B1 (fr) | Membrane conductrice de protons pour applications electrochimiques | |
DE102007034752B4 (de) | Polymerblöcke für PEM-Anwendungen | |
WO2009127614A1 (fr) | Utilisation de polymères hyperramifiés pour des applications dans des piles à combustible | |
JP2021051994A (ja) | 複合高分子電解質膜、触媒層付電解質膜、膜電極複合体および固体高分子形燃料電池 | |
DE112006003456T5 (de) | Copolymer, Polymerelektrolyt und seine Verwendung | |
DE102005043127A1 (de) | Verfahren zur Konditionierung von Membran-Elektroden-Einheiten für Brennstoffzellen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DK DZ EC EE ES FI GB GD GE GH GM HR ID IL IN IS JP KE KG KP KR KZ LC LK LS LT LU LV MA MD MG MK MN MW MZ NO NZ OM PH PL PT RO RU SD SE SI SK SL TJ TM TN TR TT TZ UA UG UZ VC VN YU ZA ZM |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE BG CH CY CZ DK EE ES FI FR GB GR IE IT LU MC PT SE SK TR BF BJ CF CG CI GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2002776768 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2002776768 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: JP |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |