CN114824391A - 一种含三唑基长侧链的聚苯醚阴离子膜及其制备方法和应用 - Google Patents
一种含三唑基长侧链的聚苯醚阴离子膜及其制备方法和应用 Download PDFInfo
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- CN114824391A CN114824391A CN202210365482.5A CN202210365482A CN114824391A CN 114824391 A CN114824391 A CN 114824391A CN 202210365482 A CN202210365482 A CN 202210365482A CN 114824391 A CN114824391 A CN 114824391A
- Authority
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- Prior art keywords
- triazole
- long side
- membrane
- side chain
- solvent
- Prior art date
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- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 55
- 150000003852 triazoles Chemical class 0.000 title claims abstract description 35
- 150000001450 anions Chemical class 0.000 title claims abstract description 26
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 38
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 8
- 150000001540 azides Chemical class 0.000 claims abstract description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 23
- 229920001955 polyphenylene ether Polymers 0.000 claims description 21
- 125000000304 alkynyl group Chemical group 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 150000001345 alkine derivatives Chemical group 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- XXFUZSHTIOFGNV-UHFFFAOYSA-N 1-bromoprop-1-yne Chemical compound CC#CBr XXFUZSHTIOFGNV-UHFFFAOYSA-N 0.000 claims description 3
- XLYOGWXIKVUXCL-UHFFFAOYSA-N 4-bromobut-1-yne Chemical compound BrCCC#C XLYOGWXIKVUXCL-UHFFFAOYSA-N 0.000 claims description 3
- SEHFYZRHGUPLSY-UHFFFAOYSA-N 5-iodopent-1-yne Chemical compound ICCCC#C SEHFYZRHGUPLSY-UHFFFAOYSA-N 0.000 claims description 3
- YITSYYQPKJETAH-UHFFFAOYSA-N 6-iodohex-1-yne Chemical compound ICCCCC#C YITSYYQPKJETAH-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- SCALDUUTBUBDKM-UHFFFAOYSA-N 4-chlorobut-1-yne Chemical compound ClCCC#C SCALDUUTBUBDKM-UHFFFAOYSA-N 0.000 claims description 2
- SGLSTFIXVDSVNV-UHFFFAOYSA-N 4-iodobut-1-yne Chemical compound ICCC#C SGLSTFIXVDSVNV-UHFFFAOYSA-N 0.000 claims description 2
- UXFIKVWAAMKFQE-UHFFFAOYSA-N 5-chloropent-1-yne Chemical compound ClCCCC#C UXFIKVWAAMKFQE-UHFFFAOYSA-N 0.000 claims description 2
- ZUKOCGMVJUXIJA-UHFFFAOYSA-N 6-chlorohex-1-yne Chemical compound ClCCCCC#C ZUKOCGMVJUXIJA-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 238000005905 alkynylation reaction Methods 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010257 thawing Methods 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims 7
- 239000000446 fuel Substances 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005349 anion exchange Methods 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000008961 swelling Effects 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- -1 hydroxide ions Chemical class 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 238000005985 Hofmann elimination reaction Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明公开了一种含三唑基长侧链的聚苯醚阴离子膜及其制备方法和应用,属于膜技术领域。该膜材料以聚苯醚作为主链,通过季铵盐炔基功能化、叠氮功能化以及Cu(I)催化叠氮化‑炔基环加成(CuAAC)反应,引入具有三唑基的长支链,离子化后制备的一种新型的碱性阴离子交换膜。通过引入具有三唑基的长支链,使膜具有良好的耐碱性、较高的离子传导率和优异的尺寸稳定性,同时三唑基团的引入,进一步提高了膜的氢氧根传导率,可作为碱性燃料电池用阴离子交换膜材料。
Description
技术领域
本发明属于膜技术领域,具体涉及一种含三唑基长侧链的聚苯醚阴离子膜及其制备方法和应用。
背景技术
聚合物电解质膜燃料电池是一类重要的新能源电池,具有绿色环保、比功率高、可靠性高、工作温度低、启动速度快等优点。聚合物电解质膜燃料电池包括质子交换膜燃料电池和氢氧根离子交换膜燃料电池。相比于质子交换膜燃料电池,氢氧根离子交换膜燃料电池工作环境为碱性,电极催化活性大大提高,从而可以选择非贵金属作为催化剂,而且催化剂更加稳定,有望解决催化剂的成本和稳定性的问题,实现聚合物电解质膜燃料电池的大规模工业化。
阴离子交换膜是碱性燃料电池的关键组成部分,制备高氢氧根传导率和化学性质稳定的阴离子交换膜至关重要,从而实现阴离子交换膜燃料电池的高功率密度和长期耐久性。各种阳离子基团功能化的聚合物骨架作为阴离子交换膜材料,如聚烯烃、聚苯乙烯,以及芳香聚合物,包括聚苯醚、聚芳醚、聚苯醚和聚醚砜。虽然近年来阴离子交换膜(AEMs)的离子电导率有了很大的提高,但由于氢氧根离子的迁移率较低,AEMs的离子电导率大多低于目前最先进的质子交换膜(如Nafion)。聚合物主链上加入更多的阳离子基团可以在一定程度上提高AEMs的离子电导率,但亲水性官能团过多则会反过来导致AEMs的吸水率过高,溶胀过度,力学性能较差。另一种提高AEMs电导率的方法是在膜上建造离子高速传输通道。通过设计具有嵌段、梳状/接枝或离子聚集结构,可诱导微相分离形态,从而促进AEMs中的离子传导。另一方面,AEMs中功能有机阳离子由于具有较强的亲核碱性工作条件,在高温下可能发生Hofmann消除、SN2亲核取代或叶立德等多次降解反应,导致离子电导率下降,因此无法满足碱性燃料电池的大规模工业化。
发明内容
有鉴于现有技术的上述缺陷,本发明旨在提高碱性燃料电池用阴离子交换膜的氢氧根传导率和化学稳定性。为实现上述目的,本发明提供了一种溶胀较小,具有合适的离子传导率和阴离子交换容量,机械性能良好的一种含三唑基长侧链的聚苯醚阴离子膜。同时,本发明还公开了含三唑基长侧链的聚苯醚阴离子膜的制备方法:即通过季铵盐炔基功能化、叠氮功能化以及Cu(I)催化叠氮化-炔基环加成(CuAAC)反应,将具有三唑基的长支链引入到聚苯醚苯环上,有效的改善了聚合物膜的离子传导率和耐碱稳定性,可作为阴离子交换膜材料。
本发明的技术方案:
本发明公开的一种含三唑基长侧链的聚苯醚阴离子膜,该含三唑基长侧链的聚苯醚阴离子膜中的含三唑基长侧链的聚苯醚(PPO-G-nQA)结构如式Ⅰ所示:
其中,m=0.1~0.9,n=1~4;G为三唑功能基团;QA为季铵盐基团;n是三唑功能基团和季铵盐氮原子之间的亚甲基数目。
进一步的,所述G三唑功能基团,有如下几种构型:
本发明所述含三唑基长侧链的聚苯醚阴离子膜的制备方法,其制备步骤如下:
(1)季铵盐的炔基功能化:在惰性气体的保护下,用三甲胺(TMA)氨基化卤素修饰的末端炔。将三甲胺溶于溶剂A中,将该溶液和卤素修饰的末端炔、溶剂B加入250mL~1L的圆底烧瓶,在20~130℃条件下反应1~24h;再将反应后的溶液进行过滤,洗涤,真空干燥,即得到炔基功能化的季铵盐QA-n;
优选的,溶剂A为四氢呋喃、二氯甲烷、氯仿、四氯化碳、二氯乙烷或1,1,2,2-四氯乙烷;
三甲胺在溶剂A中的浓度不大于20%;
卤素修饰的末端炔独立的选自6-氯-1-己炔,6-碘-1-己炔,5-氯-1-戊炔,5-碘-1-戊炔,4-氯-1-丁炔,4-碘-1-丁炔,4-溴-1-丁炔和丙炔基溴等卤素取代的末端炔;
炔基化试剂即卤素修饰的末端炔与三甲胺的摩尔比为0.2~1;
溶剂B为甲苯,乙苯,氯苯,二甲苯,三甲苯、苯乙烯、苯酚、苯胺等可以和三甲胺、溶剂A、卤素修饰的末端炔互溶或部分互溶的溶剂;
进一步的,炔基功能化的季铵盐QA-n的结构如式Ⅱ所示:
式中n是炔基和三甲胺基中N原子之间的亚甲基数目,n=1~4。
(2)Cu(I)催化叠氮化-炔基环加成(CuAAC)反应:在惰性气体气氛下,将叠氮功能化的共聚物PPO-N3-m、炔基功能化的季铵盐QA-n、催化剂、CuBr和溶剂C加入到史莱克瓶中。通过几个冷冻解冻泵循环周期进行脱气,使瓶中充满氩气,在20~100℃下搅拌2~72h。将反应后的溶液加入去离子水中,用水冲洗至少三次固体产品,除去催化剂,然后在40~100℃条件下真空干燥1~48h,即得PPO-C-nQA共聚物;
优选的,所述催化剂为五甲基二乙烯三胺(PMDETA)、三氯化铝、四氯化锡、氯化锌、三氯化铁、五氯化锑、三氟化硼、四氯化钛、氢氟酸、硫酸、五氧化二磷、磷酸、杂多酸、阳离子交换树脂、阳离子交换蒙脱土、负载型AlCl3、碳酸钾、碳酸钠、碳酸铯、氢氧化锂、氢氧化钠或氢氧化钾;
所述溶剂C为N-甲基吡咯烷酮、二甲基亚砜、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺或环丁砜;
所述溶剂C的用量为5~100mL;
所述叠氮功能化的共聚物PPO-N3-m(m=0.1~0.9)中叠氮化基团与炔基功能化的季铵盐QA-n的摩尔比为0.5~1;
所述催化剂与CuBr的摩尔比为3~0.5;
所述叠氮功能化的共聚物PPO-N3-m在溶剂C中的浓度为1%~30%;
进一步的,所述的叠氮功能化的共聚物PPO-N3-m的结构如式Ⅲ所示,
式中,m=0.1~0.9。
(3)含三唑基长侧链聚苯醚阴离子膜的制备:以PPO-G-nQA聚合物为原料,采用传统的溶液铸造法制备AEMs。将溴或碘形式的阴离子导电共聚物溶于溶剂D中配置成质量百分比浓度为3%~10%的均匀溶液,并将其倒在干净的培养皿中。在40~100℃干燥1~48h后,再在40~60℃真空干燥1~48h后获得膜。将膜浸泡在1MNaHCO3或1M NaOH中24~72h,充分置换后,再用去离子水彻底清洗,在测试前将其储存在去离子水中浸泡至中性,用流动氩气脱气30min,即得含三唑基长侧链聚苯醚阴离子膜;
优选的,所述溶剂D为二甲基亚砜、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺或N-甲基吡咯烷酮;
所得膜厚度为50±5μm。
本发明在聚苯醚侧链引入芳香结构,保持了聚苯醚良好的机械性能和热稳定性;功能基团接在烷基链上,功能基团远离了聚合物主链,减弱了OH-对功能基团进攻引起的功能基团的降解,从而提高了膜的耐碱稳定性;同时,长侧链使得此种阴离子交换膜的侧链具有相当的柔韧性,可以形成非常好的微观亲水疏水相分离,从而具有较高的阴离子传导率;更进一步的,在长侧链上引入三唑基团,可以提供了更多的水/离子传输位点,因此含三唑基团的PPO-G-nQA膜具有更高的吸水率,膜的氢氧根传导率更高,溶胀度小,力学性能及热稳定性能好的优点。
本发明的有益效果:
1.通过合成不同叠氮化功能度的聚苯醚,可以控制所制备阴离子交换膜的离子交换容量,阴离子传导性及吸水溶胀等性能;
2.本发明不同于以往的短侧链阴离子交换膜,长侧链具有更好的活动能力,有利于微观相分离的形成,提高了阴离子交换膜的OH-传导率;
3.本发明在侧链芳香基团的末端引入烷基链,并将功能基团接在烷基链上,有效降低了功能基团的降解,有利于提高阴离子交换膜的耐碱稳定性;
4.本发明在长侧链上引入三唑基团,可以提供了更多的水/离子传输位点,因此含三唑基团的阴离子交换膜具有更高的吸水率,进一步提高了膜的氢氧根传导率。
具体实施方式
以下结合技术方案,进一步说明本发明的具体实施方式。
以下为本发明的多种示例性实施方式,不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。
另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值,以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。本发明所用合成方法为本领域的常规合成方法,通过所用原料可以推定产物组成结构。
实施例1
(1)季铵盐的炔基功能化:将丙炔基溴(30mmol)、三甲基胺(150mmol溶于20mL四氢呋喃溶液中)和100mL甲苯加入250mL圆底烧瓶。室温搅拌24h后,将白色沉淀物过滤,乙醚洗涤三次,真空干燥,得到炔基功能化的季铵盐QA-1,产率为82%。
(2)Cu(I)催化叠氮化-炔基环加成(CuAAC)反应:将PPO-N3-m共聚物,m为30%(1.814mmol叠氮化基团),QA-1(2.177mmol),催化剂五甲基二乙烯三胺(PMDETA)(0.227mL,1.089mmol),CuBr(0.544mmol)和10mL的NMP加入到史莱克瓶。通过几个冷冻解冻泵循环周期进行脱气,使瓶中充满氩气,在50℃下搅拌48h。将聚合物溶液倒入去离子水中,固体产品(PPO-G-QA)用水洗几次,除去催化剂,然后在60℃下真空干燥24小时,产率为90%。
(3)膜制备与离子交换:以PPO-G-QA为原料,采用传统的溶液铸造法制备AEMs。将溴或碘形式的阴离子导电共聚物溶解在NMP(8%wt%)中,并倒在干净的培养皿上。膜在60℃条件下干燥24h后,再在60℃条件下真空干燥24h后获得。将膜浸泡在1M NaHCO3或1MNaOH中48h,分别将溴离子或碘离子交换为碳酸氢盐或氢氧根离子。处理后的膜用去离子水彻底清洗,以去除任何残留的NaHCO3或NaOH,在测试前将其储存在去离子水中,用流动氩气脱气30min。膜厚度控制在50±5μm。
经测试表明,本实施例中制备的长支链聚苯醚阴离子交换膜的含水量为25%,离子传导率为10mS·cm-1,其阴离子交换容量为1.36mmol·g-1,质量保持率为82%,拉伸强度为23.4MPa,表明本实施例中所制备的均相阴离子交换膜溶胀较小,具有合适的离子传导率和阴离子交换容量,机械性能良好。
实施例2
(1)季铵盐的炔基功能化:将4-溴-1-丁炔(30mmol)、三甲基胺(150mmol溶于20mL四氢呋喃溶液中)和100mL甲苯加入250mL圆底烧瓶。室温搅拌24h后,将白色沉淀物过滤,乙醚洗涤三次,真空干燥,得到炔基功能化的季铵盐QA-2,产率为82%。
(2)Cu(I)催化叠氮化-炔基环加成(CuAAC)反应:同实施例1,只是将实施例1步骤(2)中的QA-1替换为QA-2,得到固体产品(PPO-G-2QA)。
(3)膜制备与离子交换:同实施例1,只是将实施例1步骤(3)中的原料PPO-G-QA替换为PPO-G-2QA。
经测试表明,本实施例中所制备的长支链聚苯醚阴离子交换膜的含水量为38%,离子传导率为19mS·cm-1,其阴离子交换容量为1.61mmol·g-1,质量保持率为85%,拉伸强度为17.1MPa,表明本实施例中所制备的均相阴离子交换膜溶胀较小,具有合适的离子传导率和阴离子交换容量,机械性能良好。
实施例3
(1)季铵盐的炔基功能化:将5-碘-1-戊炔(30mmol)、三甲基胺(150mmol溶于20mL四氢呋喃溶液中)和100mL甲苯加入250mL圆底烧瓶。室温搅拌24h后,将白色沉淀物过滤,乙醚洗涤三次,真空干燥,得到炔基功能化的季铵盐QA-3,产率为82%。
(2)Cu(I)催化叠氮化-炔基环加成(CuAAC)反应:同实施例1,只是将实施例1步骤(2)中的QA-1替换为QA-3,得到固体产品(PPO-G-3QA)。
(3)膜制备与离子交换:同实施例1,只是将实施例1步骤(3)中的原料PPO-G-QA替换为PPO-G-3QA。
经测试表明,本实施例中制备的长支链聚苯醚阴离子交换膜的含水量为44%,离子传导率为24mS·cm-1,其阴离子交换容量为1.63mmol·g-1;质量保持率为81%,拉伸强度为16.7MPa,表明本实施例中所制备的均相阴离子交换膜溶胀较小,具有合适的离子传导率和阴离子交换容量,机械性能良好。
实施例4
(1)季铵盐的炔基功能化:将6-碘-1-己炔(30mmol)、三甲基胺(150mmol溶于20mL四氢呋喃溶液中)和100mL甲苯加入250mL圆底烧瓶。室温搅拌24h后,将白色沉淀物过滤,乙醚洗涤三次,真空干燥,得到炔基功能化的季铵盐QA-4,产率为82%。
(2)Cu(I)催化叠氮化-炔基环加成(CuAAC)反应:同实施例1,只是将实施例1步骤(2)中的QA-1替换为QA-4,得到固体产品(PPO-G-4QA)。
(3)膜制备与离子交换:同实施例1,只是将实施例1步骤(3)中的原料PPO-G-QA替换为PPO-G-4QA。
经测试表明,本实施例中制备的长支链聚苯醚阴离子交换膜的含水量为51%,离子传导率为33mS·cm-1,其阴离子交换容量为1.70mmol·g-1;质量保持率为84%,拉伸强度为15.7MPa表明本实施例中所制备的均相阴离子交换膜溶胀较小,具有合适的离子传导率和阴离子交换容量,机械性能良好。
实施例5
耐碱稳定性测试:将实施例2所得长支链聚苯醚阴离子交换膜浸泡在1mol/LKOH中60℃分别浸泡5d,7d后,再用去离子水浸泡至中性。
经测试表明,本实施例中所制备的长支链聚苯醚阴离子交换膜在浸泡5d,7d后,电导率保持89%,78%,表明本实施例中所制备的均相阴离子交换膜具有良好的耐碱稳定性。
性能测试:
实施例所涉及的测试方法:
IEC测试方法:取三份含三唑基长侧链的聚苯醚聚合物0.lg左右,分别浸泡在100mL,lmol/L的NaCl中24h,再分别用500mL去离子水浸泡24h洗去表面残留的NaCl。真空烘箱75℃烘干并分别称取质量记录,之后分别浸泡在25mL的0.2M NaNO3溶液中24h。最后在该溶液中加入指示剂铬酸钾溶液,并用0.1M的AgNO3溶液进行滴定,当出现砖红色沉淀并在30秒不变色即代表滴定完成。记录消耗的AgNO3溶液体积。将AgNO3溶液的浓度与体积的积除以干燥后膜的质量,即为ICE。
实施例所涉及设备:
导电率的测试:所用电化学工作站为上海辰华仪器公司出产,型号为CH1660C。
抗氧化性测试:将膜浸入80℃芬顿试剂(3wt%H2O2十4ppmFe2+)中,过一段时间将膜取出,用去离子水洗净,干燥,称重,计算膜的质量保留率x。
x=m1/m,其中,m是干膜的初始质量,m1是浸泡以后的残余质量。
燃料电池性能测试:所用仪器为美国scribner Associates co.公司生产,仪器型号为850e多量程范围燃料电池测试系统,电流模式下测试。测试条件为H2和O2完全增湿,测试温度60℃,80℃,H2和O2流速为200mL·min-1。
拉伸强度测试:采用InstronM3300电子万能试验机对湿膜样品5X0.5cm进行测试,拉伸速率5mm/min。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (10)
3.一种权利要求1所述含三唑基长侧链的聚苯醚阴离子膜的制备方法,其特征在于,其制备步骤如下:
(1)季铵盐的炔基功能化:在惰性气体的保护下,用三甲胺(TMA)氨基化卤素修饰的末端炔。将三甲胺溶于溶剂A中,将该溶液和卤素修饰的末端炔、溶剂B加入250mL~1L的圆底烧瓶,在20~130℃条件下反应1~24h;再将反应后的溶液进行过滤,洗涤,真空干燥,即得到炔基功能化的季铵盐QA-n;
(2)Cu(I)催化叠氮化-炔基环加成(CuAAC)反应:在惰性气体气氛下,将叠氮功能化的共聚物PPO-N3-m、炔基功能化的季铵盐QA-n、催化剂、CuBr和溶剂C加入到史莱克瓶中。通过几个冷冻解冻泵循环周期进行脱气,使瓶中充满氩气,在20~100℃下搅拌2~72h;将反应后的溶液加入去离子水中,用水冲洗至少三次固体产品,除去催化剂,然后在40~100℃条件下真空干燥1~48h,即得PPO-G-nQA共聚物;
(3)含三唑基长侧链的聚苯醚阴离子膜的制备:以PPO-G-nQA聚合物为原料,采用传统的溶液铸造法制备阴离子交换膜AEMs;将溴或碘形式的阴离子导电共聚物PPO-G-nQA溶于溶剂D中配置成质量百分比浓度为3%~10%的均匀溶液,并将其倒在干净的培养皿中;然后在40~100℃干燥1~48h后,再在40~60℃真空干燥1~48h后成膜;然后将膜浸泡在1MNaHCO3或1M NaOH中24~72h,充分置换后,再用去离子水彻底清洗,在测试前将其储存在去离子水中浸泡至中性,用流动氩气脱气30min,即得含三唑基长侧链聚苯醚阴离子膜;
优选的,所述溶剂D为二甲基亚砜、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺或N-甲基吡咯烷酮。
5.根据权利要求3所述含三唑基长侧链的聚苯醚阴离子膜制备方法,其特征在于,步骤(1)中所述溶剂A为四氢呋喃、二氯甲烷、氯仿、四氯化碳、二氯乙烷或1,1,2,2-四氯乙烷;所述三甲胺在溶剂A中的浓度不大于20%;
所述溶剂B为甲苯、乙苯、氯苯、二甲苯、三甲苯、苯乙烯、苯酚、苯胺等可以和三甲胺、溶剂A、卤素修饰的末端炔互溶或部分互溶的溶剂。
6.根据权利要求3所述含三唑基长侧链的聚苯醚阴离子膜制备方法,其特征在于,步骤(1)中所述卤素修饰的末端炔独立的选自6-氯-1-己炔,6-碘-1-己炔,5-氯-1-戊炔,5-碘-1-戊炔,4-氯-1-丁炔,4-碘-1-丁炔,4-溴-1-丁炔和丙炔基溴等卤素取代的末端炔;其中炔基化试剂卤素修饰的末端炔与三甲胺的摩尔比为0.2~1。
8.根据权利要求3所述含三唑基长侧链的聚苯醚阴离子膜制备方法,其特征在于,步骤(2)中,所述溶剂C为N-甲基吡咯烷酮、二甲基亚砜、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺或环丁砜;所述叠氮功能化的共聚物PPO-N3-m在溶剂C中的浓度为1%~30%;所述叠氮功能化的共聚物PPO-N3-m(m=0.1~0.9)中叠氮化基团与炔基功能化的季铵盐QA-n的摩尔比为0.5~1。
9.根据权利要求3所述含三唑基长侧链的聚苯醚阴离子膜制备方法,其特征在于,步骤(2)中所述催化剂为五甲基二乙烯三胺(PMDETA)、三氯化铝、四氯化锡、氯化锌、三氯化铁、五氯化锑、三氟化硼、四氯化钛、氢氟酸、硫酸、五氧化二磷、磷酸、杂多酸、阳离子交换树脂、阳离子交换蒙脱土、负载型AlCl3、碳酸钾、碳酸钠、碳酸铯、氢氧化锂、氢氧化钠或氢氧化钾;所述催化剂与CuBr的摩尔比为3~0.5。
10.权利要求1-9中任一权利要求所述含三唑基长侧链的聚苯醚阴离子膜或所述方法制备的阴离子膜在新能源电池中的应用,其特征在于,所述含三唑基长侧链的聚苯醚阴离子膜可在电池中作为阴离子交换膜。
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