CN111205640B - 环三磷腈六磷酸盐掺杂的聚苯并咪唑类质子交换膜制备方法 - Google Patents
环三磷腈六磷酸盐掺杂的聚苯并咪唑类质子交换膜制备方法 Download PDFInfo
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- CN111205640B CN111205640B CN202010028550.XA CN202010028550A CN111205640B CN 111205640 B CN111205640 B CN 111205640B CN 202010028550 A CN202010028550 A CN 202010028550A CN 111205640 B CN111205640 B CN 111205640B
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- Prior art keywords
- cyclotriphosphazene
- polybenzimidazole
- proton
- hexaphosphate
- mthp
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- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 57
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 57
- -1 cyclotriphosphazene hexaphosphate Chemical compound 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 33
- 239000004020 conductor Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000446 fuel Substances 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical group N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002407 reforming Methods 0.000 claims abstract 2
- 239000002131 composite material Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000002861 polymer material Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims 3
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- BYMMIQCVDHHYGG-UHFFFAOYSA-N Cl.OP(O)(O)=O Chemical compound Cl.OP(O)(O)=O BYMMIQCVDHHYGG-UHFFFAOYSA-N 0.000 claims 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 125000003373 pyrazinyl group Chemical group 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 125000002883 imidazolyl group Chemical group 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 11
- 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 9
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 9
- CGGUNVYOABLSQD-UHFFFAOYSA-N pyrazine-2,6-dicarboxylic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=N1 CGGUNVYOABLSQD-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- LSYVCAOPFHHUHM-UHFFFAOYSA-N [hydroxy-[hydroxy-[hydroxy(phosphonooxy)phosphoryl]oxyphosphoryl]oxyphosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O LSYVCAOPFHHUHM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 description 2
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 125000004185 ester group Chemical group 0.000 description 2
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
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- 230000010355 oscillation Effects 0.000 description 2
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- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- HTPGOQRGCUSPGR-UHFFFAOYSA-N phosphoric acid silane Chemical compound [SiH4].OP(O)(O)=O HTPGOQRGCUSPGR-UHFFFAOYSA-N 0.000 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 description 2
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical class OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- DPUCLPLBKVSJIB-UHFFFAOYSA-N cerium;tetrahydrate Chemical compound O.O.O.O.[Ce] DPUCLPLBKVSJIB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- SRKPIULWFNMOKI-UHFFFAOYSA-N imidazole-1,5-dicarboxylic acid Chemical compound OC(=O)C1=CN=CN1C(O)=O SRKPIULWFNMOKI-UHFFFAOYSA-N 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- CCJLMKQVMJPQNW-UHFFFAOYSA-N nitric acid;dihydrate Chemical compound O.O.O[N+]([O-])=O CCJLMKQVMJPQNW-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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Abstract
本发明报道了一种不溶性的环三磷腈基六磷酸盐(MTHP)(其中金属离子M为:Zr4+、Ce4+,Fe3+、La3+或Y3+等)作为质子导体掺杂到聚苯并咪唑(PBI)(PBI可以选用带有吡啶基团的、吡嗪基团的、咪唑基团的等)中制备了高温低湿度下使用的质子交换膜的制备方法,其特征在于,首先通过三步反应制备不溶性的环三磷腈基六磷酸盐(MTHP),用MTHP掺杂到新型的PBI中,通过交联形成复合高温、低湿度质子交换膜,该复合膜用于高温、低湿度操作的氢氧燃料电池,直接甲醇燃料电池或甲醇重整的燃料电池,高温电解,传感器等领域。
Description
技术领域
本发明涉及一种高温低湿度燃料电池中质子交换膜的制备方法,可用于固体酸催化剂、催化膜分离反应装置,燃料电池质子交换膜、电解膜、渗透膜、传感器材料等领域。
技术背景
质子交换膜燃料电池作为燃料电池的一种,因其具有环保无污染,能量转化率高,较大的功率密度以及较低的工作温度等优点受到人们的广泛关注。质子交换膜作为质子交换膜燃料电池的核心组件,它的好坏直接影响着质子交换膜燃料电池的性能及使用寿命,因此对质子交换膜的研究就显得尤为重要。为保证质子交换膜燃料电池具有较好的使用性能,就要保证质子交换膜具有高质子电导率、良好的机械性能和化学稳定性、较小的干湿变形性、低的燃料和氧化剂透过率、寿命长等性能。
PBI类质子交换膜具有良好的机械性能和抗氧化性,但其本身不导质子,因此,要先研究出具有高质子传导率的质子导体。水溶性质子导体具有较高的质子传导率,但在高湿度下易流失,使膜性能衰减,影响电池的使用寿命。因此掺杂非水溶性固态质子导体成为提高质子传导率的有效途径。无机类固体体与PBI相容性差,容易造成分相,从而影响成膜性能及机械强度。因此,开发有机-无机复合质子导体可有效解决以上问题。专利文献CN108376791A公开了一种含双质子导体的有机-无机复合质子交换膜及其制备方法,以八乙烯基笼型倍半硅氧烷和乙烯基膦酸二乙酯经加成反应得到磷酸硅烷,高温无湿条件下具有较高的质子电导率;Li等人直接采用磷酸浸泡聚苯并咪唑膜,在30%RH 180℃下,质子电导率达到了0.2S/cm(Li,X,et al.J.Power Sources(电源杂志),2018,393:99-107.)。我们曾报道了磺化苯膦酸盐掺杂的复合质子交换膜(李忠芳等,(ZL200810160560.8;ZL200810160561.2;ZL 201110025204.7)。
本发明是用不溶性的环三磷腈基六磷酸盐(MTHP)作为质子导体掺杂到碱性高分子材料PBI中,使用交联剂交联制备复合膜。该复合膜具有耐高温性能好、在低湿度下电导率高,机械性能、抗氧化性能好,干湿变形性能小、甲醇扩散系数小等优点。
六氯环三磷腈由于磷氯键的活泼性,可以使氯很容易被取代,可以多种化合物反应,制得一系列相关化合物。另外由于六元环的稳定性,使其具有耐酸耐碱,以及耐高温特性。聚磷腈类化合物本身具有大量能起到阻燃效果的磷、氮元素,可起到良好的阻燃作用。例如专利文献CN 201410536145.3唐林生等公开制备的三聚氰胺改性聚氨基环三磷腈的水溶性和吸水性明显降低,热稳定性明显提高,初始热分解温度由70℃左右提高到200℃以上,可作为良好的阻燃剂;CN201910160816.3宋伟国等公开了含磷酸酯的环三磷腈衍生物的制备方法及应用,制得的化合物具有良好的阻燃效果,添加少量该化合物即可达到很好的阻燃效果,同时热稳定性好加热不易分解,可作为一种良好的阻燃剂使用。共价交联,是一种有效的交联方式,能明显提高膜的机械强度。环氧树脂作为常用的交联剂引起人们的广泛兴趣。交联剂的使用与其交联度有关,PBI膜的机械,尺寸和化学稳定性通常随着交联度的增加而增加,过量的使用交联剂,会使质子导体相对含量降低,这降低了酸掺杂能力,从而降低了质子传导率。在保证膜具有良好的机械强度下,使交联度含量相对较低,为提高质子导体掺杂量,可对PBI进行共价交联。利用双或多官能度的交联剂,与聚合物进行反应,通过共价键将聚合物链彼此连接,形成三维的交联网络结构的聚合物修饰方法。共价交联一般可以提高PBI膜的机械性能、抗氧化性能和阻醇性能,改善其干湿变形性。
发明内容
针对现有技术的不足,本发明制备了一种高磷酸含量的环三磷腈基六磷酸,其与可溶性高价金属离子的盐反应,制备不溶性的磷酸盐作为有机-无机质子导体材料用于掺杂到聚苯并咪唑类碱性高分子材料中制备高温低湿度质子交换膜,以解决磷酸掺杂已流失等问题,增加复合膜的耐久性。
本发明的技术方案如下:
1.环三磷腈基六磷酸盐耐高温质子导体的制备方法。首先,以HCCP与亚磷酸酯为原料,在无催化剂、无溶剂的条件下,在环三磷腈基母体上通过一步反应引入六个磷酸酯基,直接合成环三磷腈基六磷酸酯(RTHP)。然后,在浓盐酸中对其进行水解,得到环三磷腈基六磷酸(THP)。在水相中,将THP与金属(如铈、锆、铁等)的水溶性盐进行聚合反应,即可制备其盐MTHP。本发明提供的MTHP的制备工艺具有原料廉价易得、工艺简单、条件温和、产率高和后处理简单的优势。这样制备的MTHP具有良好的耐温性能,制备方法简便。更重要的是,由于在反应的第一步中,在环三磷腈基母体上一步引入了六个磷酸酯基,使THP结构中,每个环三磷腈基母体都含六个磷酸基,从空间取向上,六个磷酸基在环三磷腈基母体上互为间位,彼此之间位阻最小,有利于活性基团的充分暴露。在与金属盐反应时,通过二者摩尔比的控制,可以调控磷酸基上多少羟基参与聚合反应,多少羟基暴露出来。参与聚合反应的羟基使产物形成聚合物骨架,且在水中不能溶解,避免使用过程中发生流失;未反应而暴露出的羟基则可以提供酸性和氢键供体,使其具有催化活性、质子传导性能。制备过程的反应方程式如下:
本质子导体合成工艺和性能方面具有如下优点:
(1)合成工艺上的优点。本发明提供的六磷酸基耐高温质子导体的制备工艺,可以在环三磷腈基母体上一步引入六个磷酸基,所用原料廉价易得,制备工艺简单,条件温和,后处理简便,环境友好,产率高。
(2)产品性能上的优点。本发明所制备的耐高温质子酸具有良好的热稳定性、传感性能、催化性能和离子传导性能。
(3)本发明制备的磷酸基耐高温质子酸,其酸度以及氢键给体和受体的含量可调节,具有一定的吸水性,容易电离构筑离子键,也便于形成氢键网络结构,通过氢键的断裂-形成过程进行质子传导,在中高温和不同湿度尤其是低湿度下具有良好的质子传导性能。另外,其有机-无机复合结构能提高其与聚合物的相容性,避免出现相分离。
2.环三磷腈基六磷酸盐掺杂新型PBI交联复合膜的制备
(1)含有吡啶基团的聚苯并咪唑(PPBI)的制备:用2,6-吡啶二甲酸与3,3’-二氨基联苯胺(DABz)反应制备,具体反应步骤为:在装有电动搅拌和氮气保护的三口烧瓶中加入多聚磷酸(PPA)(100g),氮气保护下160℃搅拌1h以除去多余的水分及空气。将DABz(4.00g,18.7mmol)以及2,6-吡啶二甲酸(3.12g,18.7mmol)混合均匀,慢慢加入到三口烧瓶中。控制氮气流速,防止DABz被氧化,同时将反应温度提升到200℃并继续保温、搅拌反应5~8h。随着反应时间的增加,聚合体系逐渐变得粘稠。待粘度合适时停止反应,反应混合液慢慢转移到大量去离子水中抽丝,洗净、烘干,粉碎,去离子水多次洗涤以除去多聚磷酸和未反应的反应物,即得到PPBI,用乌氏粘度计测定PPBI的分子量。其粘均分子量为4.5万到5万。
(2)其它带吡啶基团的PBI的制备方法:同(1)的方法,只是将2,6-吡啶二甲酸分别换成2,5-吡啶二甲酸或2,3-吡啶二甲酸即可,其它操作同(1),即可得到含有不同吡啶基团的PPBI,产品分别记为:2,5-PPBI或2,3-PPBI。
(3)其他PBI制备方法同合成实验中的(1)部分。只是将2,6-吡啶二羧酸改为其他二羧酸(如,间苯二甲酸、2,6-吡嗪二甲羧酸、2,3-吡嗪二甲酸、2,5-吡嗪二甲酸等),ABPBI的制备是用3,4-二氨基苯甲酸替代2,6-吡啶二甲酸与3,3’-二氨基联苯胺(DABz)两种原料,只用3,4-二氨基苯甲酸即可。
3.制膜工艺采用流延法;为了提升膜的机械性能、抗氧化性能,改善其干湿变形性采用了交联剂进行交联。交联剂选用多官能度的交联剂。
4.复合膜的高温低湿度质子交换膜的制备
(1)以ZrTHP掺杂到聚苯并咪唑(PPBI)的复合质子交换膜的制备为例:以ZrTHP掺杂30%为例。取1.0g PPBI加入10mL N,N’-二甲基乙酰胺(DMAc)中,在80℃下磁力搅拌24h使其充分溶解,抽滤除去不溶物。在50℃下向滤液中加入交联剂0.05g 1,3,5-三(环氧乙烷-2-基甲基)-1,3,5-三嗪-2,4,6-三酮(异氰尿酸三缩水甘油酯,TGIC),继续搅拌2.5h使其充分溶解。再加入0.52g ZrTHP的钠盐,继续搅拌3h使其充分分散在铸膜液中。超声振荡1h以除去气泡,而后将其浇铸在玻璃板上,在60℃下流延12h,120℃下加热12h除去溶剂,而后在160℃下加热6h使PPBI和TGIC进行充分交联。将得到的膜在0.1mol L-1H2SO4水溶液中室温下浸泡24h,使掺杂到膜中的ZrTHP的钠盐充分酸化为ZrTHP,而后在去离子水中浸泡24h(每6h换水一次)以洗去膜中的硫酸,得到PPBI-TGIC(5%)/ZrTHP(30%)复合膜。
其它MTHP掺杂的膜的制备方法同上,只是将ZrTHP替换成MTHP即可。
本发明的创新点:
(1)本发明所用的质子导体是不溶性的含有多磷酸基团、且空间分布均匀的环三磷腈基六磷酸盐,其盐为聚合物,且分子中还有多个未反应的羟基,可用于质子导体,且不易流失。
(2)该盐是有机-无机复合的质子导体材料,可以与高分子材料混合均匀,不分相。
(3)质子导体与碱性高分子材料PBI之间可以形成盐键或氢键,其复合膜内的氢键网络可以形成质子的传递通道,该质子通道起到在高温、低湿度下质子传导的作用。质子导体不溶于水,且为聚合物,所以,质子导体不会流失,复合膜的电导率不会随着时间的延长而降低,复合膜的耐久性优良。
(4)由于高温质子导体分子中各基团均具有很好的耐温性能,所以该复合膜可以在低湿度、250℃下使用,当然,在低温下也有很好的电导率,所以该复合膜适用的温度范围是-15℃到250℃,相对湿度范围0到50%。
为了更好地提高复合膜的机械性能、抗氧化性能以及提升复合膜的干湿变形性,本发明采用多官能度的交联剂对PBI分子之间进行交联,以得到体型的高分子材料,从而提高膜的机械性能、抗氧化性能,改善其干湿变形性。由于采用多官能度的交联剂,所以交联剂的添加量可以比较小,且交联效果很好。
具体实施方式
[实施例1]:ETHP的制备:
将20.9g HCCP(0.06mol)在搅拌下2h内分三批慢慢加入60mL亚磷酸三乙酯(TEP,0.34mol)中,升温至120℃反应6h,冷却后加入石油醚静置过夜,得到的沉淀抽滤得到黄色固体,即环三磷腈基六元磷酸乙酯(ETHP),产率86%。
采用相同反应步骤,以不同亚磷酸酯或在不同条件进行反应的产率列于下表1所示:
表1不同亚磷酸酯反应制备RTHP的反应条件及产率
[实施例2]:THP的制备:
将46.5g ETHP(0.05mol)加入100mL浓盐酸中,磁力搅拌下回流72h,冷却至50℃,减压蒸去HCl,浓缩至40mL,用90mL乙酸乙酯萃取三次,以除去未水解的TTP。将水相浓缩至近干,在真空干燥箱中120℃下干燥至恒重,得到29.5g白色固体,即六磷酸基环三磷腈(THP,产率:95%)。
采用相同反应步骤,只是用二氯甲烷、苯、甲苯或石油醚萃取,产率分别为89%,85%,87%和82%。
采用相同的反应步骤,在浓盐酸中回流24h,在70℃下减压蒸馏,用乙酸乙酯萃取,产率为71%。
不同酯基的RTHP水解反应结果如表2所示。
表2不同酯基的RTHP水解制备THP的产率
[实施例3]:CeTHP-1:2的制备
取24.8g THP(0.04mol)加入60mL去离子水中,室温搅拌1h使其充分溶解。取11.0g二水合硝酸铈铵(0.02mol)溶于50mL 0.1mol L-1稀盐酸中(避免水解生成难溶的氢氧化高铈)。将硝酸铈铵的盐酸溶液滴加到THP的水溶液中,室温搅拌12h,使THP上的磷酸基与Ce4+之间充分进行聚合反应,得到黄色悬浊液。离心,用去离子水洗涤至滤液pH=7,以充分除去未反应的原料,在120℃下干燥12h,得24.3g黄色固体(产率86%),其中铈和THP的摩尔比为1:2,记为CeTHP-1:2。
其它配比的铈盐的制备同上,只是改变铈盐与THP摩尔比,其结果见表3所示。采用其他高价金属离子的可溶性盐替代硝酸铈铵所制备的MTHP盐,制备工艺条件和性能如表3,表4所示。
[实施例4]:以CeTHP-1:2作为质子导体,在180℃,100%相对湿度下质子电导率达0.147S/cm;在180℃,50%相对湿度下质子电导率达0.086S/cm;在180℃,干燥条件下质子电导率达0.041S/cm。采用其他高价金属离子的可溶性盐替代硝酸铈铵所制备的MTHP盐,其压片测的的电导率如表4所示。
[实施例5]:以CeTHP-1:2作为质子导体用于高温质子交换膜的制备。
(1)含有吡嗪基团的聚苯并咪唑(PzPBI)的制备:用2,6-吡嗪二甲酸与3,3’-二氨基联苯胺(DABz)反应制备,具体反应步骤为:在装有电动搅拌和氮气保护的三口烧瓶中加入多聚磷酸(PPA)(100g),氮气保护下160℃搅拌1h以除去多余的水分及空气。将DABz(4.00g,18.7mmol)以及2,6-吡嗪二甲酸(3.14g,18.7mmol)混合均匀,慢慢加入到三口烧瓶中。控制氮气流速,防止DABz被氧化,同时将反应温度提升到200℃并继续保温、搅拌反应5~8h。随着反应时间的增加,聚合体系逐渐变得粘稠。待粘度合适时停止反应,反应混合液慢慢转移到大量去离子水中抽丝,洗净、烘干,粉碎,去离子水多次洗涤以除去多聚磷酸和未反应的反应物,即得到PzPBI,用乌氏粘度计测定PzPBI的分子量。其粘均分子量为4.5万到5.5万。
(2)其它带吡嗪基团的PBI的制备方法:同(1)的方法,只是将2,6-吡嗪二甲酸分别换成2,5-吡嗪二甲酸或2,3-吡嗪二甲酸即可,其它操作同(1),即可得到含有不同吡啶基团的PzPBI,产品分别记为:3,5-PzPBI或2,3-PzPBI。带有其它基团的PBI的制备方法同(1)的步骤,只是将2,6-吡嗪二甲酸用其它带有芳香环的二羧酸即可。
(3)CeTHP-1:2掺杂到聚苯并咪唑(PzPBI)的复合质子交换膜的制备:以CeTHP-1:2掺杂40%为例。取1.0g PzPBI加入10mL N,N’-二甲基乙酰胺(DMAc)中,在80℃下磁力搅拌24h使其充分溶解,抽滤除去不溶物。在50℃下向滤液中加入交联剂0.05g TGIC,继续搅拌2.5h使其充分溶解。再加入0.70g CeTHP-1:2的钠盐,继续搅拌3h使其充分分散在铸膜液中。超声振荡1h以除去气泡,而后将其浇铸在玻璃板上,在60℃下流延12h,120℃下加热12h除去溶剂,而后在160℃下加热6h使PBI和TGIC进行充分交联。将得到的膜在0.1mol L- 1H2SO4水溶液中室温下浸泡24h,使掺杂到膜中的CeTHP-1:2的钠盐充分酸化为CeTHP-1:2,而后在去离子水中浸泡24h(每6h换水一次)以洗去膜中的硫酸,得到PzPBI-TGIC(5%)/CeTHP-1:2(40%)复合膜。
[实施例6]:其它PBI制备方法同实施例5中的(1)部分。只是将2,6-吡嗪二羧酸改为其它二羧酸(如,间苯二甲酸、2,6-吡啶二羧酸、1,8-萘二羧酸,1,5-咪唑二羧酸或4,4’-联苯二甲酸等)
[实施例7]:其它交联剂交联,其他CeTHP-1:2掺杂量的PBI复合膜的制备方法同实施例5中实验(3)部分,只是把交联剂TGIC改为其它交联剂,CeTHP-1:2的用量0.7g改为其它量即可。其复合膜不同相对湿度下的电导率测试结果与表5所示,复合膜相对湿度50%,不同温度下的电导率测试结果与表6所示
[实施例8]:膜电极的制备及单电池性能测试。同传统工艺和方法制备膜电极(MEA),只是用本发明的高温复合膜替代Nafion膜。制备的膜电极组装单电池,进行电池性能测试。按照单电池组装的方法,把制备的膜电极组装成单电池并且连接到燃料电池测试系统进行测试,阳极用相对湿度为50%的氢气为燃料,流速40mL/min,电池的工作温度150℃,阴极用氧气流速20mL/min,背压0.2MPa。电池性能测试前首先进行活化,再测试其性能。不同膜的MEA测试结果如表7所示。
表3 MTHP类质子导体的制备工艺条件及性能对比
注:IEC的单位为meq·g-1。
表4 MTHP类质子导体在180℃下不同性低湿度下的质子电导率(S/cm)
表5 MTHP掺杂到PBI制备的复合膜在不同性低湿度下的质子电导率(S/cm)
注:2,6-PzPBI:2,6-吡嗪二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,5-TpPBI:2,5-噻吩二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,6-PyPBI:2,6-吡啶二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
表6 MTHP掺杂PBI复合膜在RH50%不同温度下的质子电导率(S/cm)
注:2,6-PzPBI:2,6-吡嗪二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,5-TpPBI:2,5-噻吩二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,6-PyPBI:2,6-吡啶二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
多官能度的交联剂缩写及中文全称:
TGIC:1,3,5-三(环氧乙烷-2-基甲基)-1,3,5-三嗪-2,4,6-三酮
TGDDM:N,N,N’,N’-四环氧丙基-4,4’-二氨基二苯甲烷
CMPSU:氯甲基化聚醚砜
CMPBI:氯甲基化聚苯并咪唑
PDCP:聚二氯磷腈
表7 MTHP掺杂PBI复合膜制备的膜电极的性能
注:2,6-PzPBI:2,6-吡嗪二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,6-PyPBI:2,6-吡啶二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI
2,3-PzPBI:2,3-吡嗪二甲酸与3,3’-二氨基联苯胺缩合得到的新型PBI多官能度的交联剂缩写及中文全称:
TGIC:1,3,5-三(环氧乙烷-2-基甲基)-1,3,5-三嗪-2,4,6-三酮
TGDDM:N,N,N’,N’-四环氧丙基-4,4’-二氨基二苯甲烷
CMPSU:氯甲基化聚醚砜
PDCP:聚二氯磷腈。
Claims (4)
1.环三磷腈六磷酸盐掺杂的聚苯并咪唑类质子交换膜制备方法,其特征在于:用耐高温的、不溶性的环三磷腈基六磷酸盐MTHP作为质子导体掺杂到聚苯并咪唑PBI通过交联制备高温、低湿度下使用的质子交换膜,其制备过程包括:
(1)以六氯环三磷腈HCCP为原料与亚磷酸酯反应,得到环三磷腈基六磷酸酯RTHP,在浓盐酸中水解得到环三磷腈基六元磷酸THP,将六元磷酸在水相中与高价过渡金属离子发生反应得到不溶于水的环三磷腈基六磷酸高价过渡金属离子盐MTHP:将HCCP在搅拌下1~2h内分批慢慢加入亚磷酸酯中,升温至90~140℃反应6~12h,冷却后加入石油醚中过夜,抽滤得到RTHP;将RTHP在浓盐酸中加热、搅拌、回流反应24~72h,在60℃~70℃下,减压蒸出HCl、醇和水,用水和有机溶剂萃取,将水相浓缩,真空干燥得THP;将THP溶于水,按照一定的比例加入高价过渡金属离子的水溶性的盐,搅拌反应12~24h,将得到的沉淀抽滤、洗涤至pH为7,得到不溶于水的MTHP;
(2)聚苯并咪唑的制备是用3,3’-二氨基联苯胺与含有碱性基团的芳香二酸为原料,在多聚磷酸中,惰性气体保护下,200℃,反应3~8h,得到聚苯并咪唑,其粘均分子量为4.5~5万;
(3)采用流延成膜法制备复合膜,按照质子导体掺杂量20wt%~60wt%,用多官能度的交联剂进行交联制备复合膜;
制备的复合质子交换膜在-15℃~250℃,相对湿度0~50%下使用,其膜电极制备过程中也用相应的MTHP的作为质子添加剂,用于高温氢-空气燃料电池、直接甲醇燃料电池或甲醇重整的燃料电池;燃料电池对氢气或氧气的纯度要求降低。
2.权利要求1所述的环三磷腈六磷酸盐掺杂的聚苯并咪唑类质子交换膜制备方法,其特征在于:MTHP中的Mn+是Zr4+,Fe3+,La3+或Y3+中的一种或几种的混合物;MTHP是不溶性的盐,是有机-无机杂化材料,耐高温,其中,未参与反应的磷酸或磷酸基团上未参与反应的羟基表现出酸性,用于不溶性的耐高温的质子导体。
3.权利要求1所述的环三磷腈六磷酸盐掺杂的聚苯并咪唑类质子交换膜制备方法,其特征在于:所用的聚苯并咪唑类高分子材料是含有吡嗪、吡啶或咪唑类碱性基团的聚苯并咪唑,这些PBI有更多的碱性基团,掺杂质子导体量会增加,制备的复合膜的质子电导率会更高;选用其PBI分子中含有多个2,6-吡啶基团、2,3-吡啶基团、2,4-吡啶基团,2,5-吡啶基团;2,6-吡嗪基团、2,3-吡嗪基团、2,4-吡嗪基团,2,5-吡嗪基团;2,3-咪唑基团、2,5-咪唑基团的一种或几种的混合基团。
4.权利要求1所述的环三磷腈六磷酸盐掺杂的聚苯并咪唑类质子交换膜制备方法,其特征在于:交联剂选用多官能度的交联剂,多官能度以在同等交联的情况下所用交联剂最少,对复合膜的电导率影响最小;交联剂选用三或四环氧值的环氧树脂、高氯含量的氯甲基化聚醚砜、氯甲基化聚苯并咪唑或聚二氯磷腈。
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