CN117586467A - Ion-conducting cross-linked material, preparation method thereof, anion exchange membrane and application thereof - Google Patents
Ion-conducting cross-linked material, preparation method thereof, anion exchange membrane and application thereof Download PDFInfo
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- CN117586467A CN117586467A CN202410080553.6A CN202410080553A CN117586467A CN 117586467 A CN117586467 A CN 117586467A CN 202410080553 A CN202410080553 A CN 202410080553A CN 117586467 A CN117586467 A CN 117586467A
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011243 crosslinked material Substances 0.000 title claims description 38
- 150000002500 ions Chemical class 0.000 claims abstract description 82
- 125000003277 amino group Chemical group 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000004132 cross linking Methods 0.000 claims abstract description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 19
- 239000002322 conducting polymer Substances 0.000 claims description 78
- 229920001940 conductive polymer Polymers 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 125000000217 alkyl group Chemical group 0.000 claims description 66
- 125000003118 aryl group Chemical group 0.000 claims description 63
- 239000000126 substance Substances 0.000 claims description 50
- 239000003431 cross linking reagent Substances 0.000 claims description 48
- -1 halogen ion Chemical class 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 32
- 150000003839 salts Chemical group 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 28
- 125000005843 halogen group Chemical group 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000001450 anions Chemical class 0.000 claims description 20
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- 238000011282 treatment Methods 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 9
- 229930184652 p-Terphenyl Natural products 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 claims description 6
- 238000012983 electrochemical energy storage Methods 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 4
- 125000005587 carbonate group Chemical group 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
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- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000909 electrodialysis Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 claims description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-O 1H-indol-1-ium Chemical compound C1=CC=C2[NH2+]C=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-O 0.000 claims description 2
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical class C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 230000008961 swelling Effects 0.000 abstract description 37
- 239000003513 alkali Substances 0.000 abstract description 27
- 230000005518 electrochemistry Effects 0.000 abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 238000006073 displacement reaction Methods 0.000 description 26
- 239000007787 solid Substances 0.000 description 26
- 239000002904 solvent Substances 0.000 description 24
- 238000007334 copolymerization reaction Methods 0.000 description 22
- 230000009286 beneficial effect Effects 0.000 description 19
- 238000005266 casting Methods 0.000 description 19
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 235000011118 potassium hydroxide Nutrition 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 125000003386 piperidinyl group Chemical group 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- ZABBFAHZPHMIJC-UHFFFAOYSA-N 1,1-Dibromopropan-2-one Chemical compound CC(=O)C(Br)Br ZABBFAHZPHMIJC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 6
- 125000005936 piperidyl group Chemical group 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 235000011181 potassium carbonates Nutrition 0.000 description 6
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- CSVFWMMPUJDVKH-UHFFFAOYSA-N 1,1-dichloropropan-2-one Chemical compound CC(=O)C(Cl)Cl CSVFWMMPUJDVKH-UHFFFAOYSA-N 0.000 description 4
- PTBPTNCGZUOCBK-UHFFFAOYSA-N 2,4,5-trimethyl-1h-imidazole Chemical compound CC1=NC(C)=C(C)N1 PTBPTNCGZUOCBK-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
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- 238000001914 filtration Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 2
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
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- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
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- 125000001246 bromo group Chemical group Br* 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
-
- 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
- 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
- C08J5/2287—After-treatment
-
- 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
-
- 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
-
- 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
- H01M8/1055—Inorganic layers on the polymer electrolytes, e.g. inorganic coatings
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
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- 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
- Y02E60/10—Energy storage using batteries
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- 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
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Abstract
The application provides an ion conduction cross-linked product, a preparation method thereof, an anion exchange membrane and application thereof, and belongs to the technical field of electrochemistry. According to the method, the cross-linking structure in the ion-conducting cross-linked matter is adjusted to enable the cross-linking structure to be of a structure containing amino groups or/and positively charged ammonium groups, and the ion-conducting cross-linked matter is adopted to prepare the anion-exchange membrane, so that the ion conductivity of the anion-exchange membrane can be improved, and the anion-exchange membrane has good electrochemistry; the swelling rate of the anion exchange membrane can be reduced, and the alkali stability of the anion exchange membrane can be improved, so that the anion exchange membrane has longer service life, and the application range of the anion exchange membrane is widened to a great extent.
Description
Technical Field
The application relates to the technical field of electrochemistry, in particular to an ion conduction cross-linked product, a preparation method thereof, an anion exchange membrane and application thereof.
Background
The application of the anion exchange membrane is mainly influenced by the electrochemical performance and the service life of the anion exchange membrane; wherein the service life of the anion exchange membrane is mainly influenced by the swelling rate and the alkali stability of the anion exchange membrane. However, the existing anion exchange membrane cannot have better electrochemical performance (such as lower ion conductivity, etc.), alkali stability and lower swelling rate, so that the anion exchange membrane cannot meet the higher requirements of continuous development of technology, and the application of the anion exchange membrane is greatly limited.
Disclosure of Invention
The invention aims to provide an ion conduction cross-linked matter, a preparation method thereof, an anion exchange membrane and application thereof, which aim to improve the electrochemical performance and the service life of the existing anion exchange membrane, so that the anion exchange membrane has higher ion conductivity, lower swelling rate and higher alkali stability.
In a first aspect, the present application provides an ion-conducting cross-link having the structural formula:
。
wherein m is 1 And m 2 Are all greater than or equal to 0, n 1 And n 2 All > 0, p 1 And p 2 All > 0, p 3 And p 4 All are more than or equal to 0; x and y are each independently 0 or 1, s and q are each not less than 0, x and s are not simultaneously 0, and y and q are not simultaneously 0; j and u are each independently 0 or 1, k and a are each 0 or more, j and k are not simultaneously 0, u and a are not simultaneously 0; ar (Ar) 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 Ar, ar 8 Each independently selected from substituted or unsubstituted aryl; r is R 1 、R 6 、R 7 、R 12 、R g R is as follows r Each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; r is R 2 R is as follows 8 Are all groups containing fluorine atoms; r is R 30 R is as follows 31 All are halogen atoms; r is R a R is as follows b Each independently is of the structure ofOr->；R 3 R is as follows 4 Each independently selected from the group consisting of substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, structures containing salt units, and hydrogen atoms; x is X 1 - X is as follows 2 - Are anions; w is a natural number of 1 to 6; r is R f R is as follows h Each independently selected from the group consisting of a structure containing a salt unit, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a group containing a halogen atom; r is R 5 R is as follows 11 Each independently selected from the group consisting of a structure comprising salt units, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a group comprising a halogen atom, a group comprising +.>Structure of (C) containing->Is of a structure of (2); m is M 1 、M 2 M is as follows 3 Are all cross-linked structures; the cross-linked structure contains an amine group, or the cross-linked structure contains a positively charged ammonium group and an anion electrostatically bound to the positively charged ammonium group; p (P) 1 Is a first ion-conducting polymer, P 2 Is a second ion conducting polymer.
According to the method, the cross-linking structure in the ion-conducting cross-linked matter is adjusted to enable the cross-linking structure to be of a structure containing amino groups or/and positively charged ammonium groups, and the ion-conducting cross-linked matter is adopted to prepare the anion-exchange membrane, so that the ion conductivity of the anion-exchange membrane can be improved, and the anion-exchange membrane has good electrochemistry; the swelling rate of the anion exchange membrane can be reduced, and the alkali stability of the anion exchange membrane can be improved, so that the anion exchange membrane has longer service life, and the application range of the anion exchange membrane is widened to a great extent.
In a second aspect, the present application provides a method of making an ion-conducting cross-link comprising: carrying out a crosslinking reaction on a system containing an ion conducting polymer and a crosslinking agent; the cross-linking agent is a cross-linking agent containing amino groups; the structural formula of the ion conducting polymer is as follows:
. Or, the preparation method of the ion-conducting crosslinked material comprises the following steps: carrying out a crosslinking reaction on a system containing a first polymer and a crosslinking agent; then adding a salifying substance into the crosslinked system for salifying reaction; the cross-linking agent is a cross-linking agent containing amino groups; the first polymer has the following structural formula:
. Wherein m is greater than or equal to 0, n is greater than 0, p is greater than 0, and x 1 0 or 1, s 1 Not less than 0 and x 1 And s 1 Not simultaneously 0; ar (Ar) 1a 、Ar 2a Ar, ar 3a Each independently selected from substituted or unsubstituted aryl; r is R 1a R is as follows 6a Each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; r is R 2a Is a group containing a fluorine atom; r is R 5a A group selected from the group consisting of a structure containing a salt unit, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a halogen atom; r is R 30 Is a halogen atom; r is R a1 The structural formula is as follows: />Or (b)；R c The structural formula is as follows: />Or->The method comprises the steps of carrying out a first treatment on the surface of the The salt-forming substance comprises a first substance or/and a second substance, the first substance The structural formula of the matter is R d -R 39 The structural formula of the second substance is->；R 3a R is as follows 4a Each independently selected from the group consisting of substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, structures containing salt units, and hydrogen atoms; x is X 1a - X is as follows 2a - Are anions; w (w) 1 A natural number of 1 to 6; r is R d Selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted aryl, R 39 、R 9 R is as follows 10 Each independently selected from a halogen atom, a carbonate group or a sulfate group.
In a third aspect, the present application provides an anion exchange membrane comprising an ion-conducting cross-link; or, the anion exchange membrane comprises a porous supporting layer and a filler filled in the pores of the porous supporting layer, wherein the filler comprises inorganic hydrophilic particles and ion conduction cross-linking substances; or, the anion exchange membrane comprises a porous supporting layer and a filler filled in the pores of the porous supporting layer, wherein the filler comprises an ion conduction cross-link; alternatively, the anion exchange membrane comprises inorganic hydrophilic particles and ion-conducting crosslinks. Wherein the ion-conducting crosslinked material is the ion-conducting crosslinked material provided in any one of the above-mentioned first aspects or the ion-conducting crosslinked material produced by the production method of the ion-conducting crosslinked material provided in any one of the above-mentioned second aspects.
In a fourth aspect, the present application provides a use of an anion exchange membrane provided in the third aspect above for the preparation of an electrolyzed water device, an electrodialysis device, a fuel cell or an electrochemical energy storage device; the electrochemical energy storage device comprises a flow battery.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of an ion conducting polymer prepared in the step (2) of example 1 of the present application.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the ion-conducting cross-linked product prepared in step (3) of example 1 of the present application.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the ion-conducting cross-linked product prepared in step (3) of example 2 of the present application.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of 4 '-bis (2, 4, 5-trimethyl-1H-imidazole) -1,1' -biphenylene of example 3 of the present application.
FIG. 5 is a nuclear magnetic resonance spectrum of the ion-conducting cross-linked product obtained in the step (3) of example 4 of the present application.
FIG. 6 is a nuclear magnetic resonance spectrum of an ion-conducting polymer prepared in step (2) of example 5 of the present application.
FIG. 7 is a nuclear magnetic resonance spectrum of an ion-conducting polymer prepared in step (2) of example 6 of the present application.
FIG. 8 is a nuclear magnetic resonance spectrum of an ion-conducting polymer prepared in step (2) of example 7 of the present application.
FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of the ion conducting polymer prepared in step (2) of comparative example 1 of the present application.
Detailed Description
The aryl piperidinium backbone is the most widely studied polymer backbone structure in the field of anion exchange membranes. In order to reduce the swelling rate of an anion exchange membrane having an arylpiperidinium skeleton, the piperidine structure of the polymer main chain structure is generally modified. However, the inventors found that modification of the piperidine structure on the polymer backbone structure results in conformational stability of the six-membered ring in the piperidine structure on the polymer backbone structure under basic conditions, which in turn results in poor base stability of the aryl piperidinium backbone anion exchange membrane.
An ideal anion exchange membrane should combine higher ion conductivity, lower swelling and higher oxidation resistance, in order to enable the anion exchange membrane to combine higher ion conductivity, lower swelling and higher alkali stability, an ion-conducting cross-link is provided having the following structural formula:
。
wherein m is 1 And m 2 Are all greater than or equal to 0, n 1 And n 2 All > 0, p 1 And p 2 All > 0, p 3 And p 4 All are more than or equal to 0; x and y are each independently 0 or 1, s and q are each not less than 0, x and s are not simultaneously 0, and y and q are not simultaneously 0; j and u are each independently 0 or 1, k and a are each ≡0, and j and k are not 0 at the same time, u and a are not 0 at the same time. Ar (Ar) 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 Ar, ar 8 Each independently selected from substituted or unsubstituted aryl groups. R is R 1 、R 6 、R 7 、R 12 、R g R is as follows r Each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl. R is R 2 R is as follows 8 Are groups containing fluorine atoms. R is R 30 R is as follows 31 Are halogen atoms. R is R a R is as follows b Each independently is of the structure ofOr->；R 3 R is as follows 4 Each independently selected from the group consisting of substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, structures containing salt units, and hydrogen atoms; x is X 1 - X is as follows 2 - Are anions; w is a natural number of 1 to 6. R is R f R is as follows h Each independently selected from the group consisting of a structure containing a salt unit, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a group containing a halogen atom. R is R 5 R is as follows 11 Each independently selected from the group consisting of a structure comprising salt units, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a group comprising a halogen atom, a group comprising +.>Structure of (C) containing->Is a structure of (a). M is M 1 、M 2 M is as follows 3 Are all cross-linked structures; the crosslinked structure containing amine groups, or the crosslinked structure containing positive strapsAn electric ammonium group and an anion electrostatically bound to the positively charged ammonium group. P (P) 1 Is a first ion-conducting polymer, P 2 Is a second ion conducting polymer.
According to the ion-conducting cross-linked matter provided above, M 1 The structure of the two ion-conducting polymers connected is (A) 1 )m 1 -(B 1 )n 1 -(C 1 )p 3 -(D 1 )p 1 (A) 2 )m 2 -(B 2 )n 2 -(C 2 )p 4 -(D 2 )p 2 ；(A 1 )m 1 -(B 1 )n 1 -(C 1 )p 3 -(D 1 )p 1 Is not limited to A in ion-conducting polymers 1 、B 1 、C 1 D (D) 1 The order of attachment of these four copolymerized units is such that the ion-conducting polymer may contain A 1 、B 1 、C 1 D (D) 1 The four copolymerization units are needed; (A) 2 )m 2 -(B 2 )n 2 -(C 2 )p 4 -(D 2 )p 2 Is not limited to A in ion-conducting polymers 2 、B 2 、C 2 D (D) 2 The order of attachment of these four copolymerized units is such that the ion-conducting polymer may contain A 2 、B 2 、C 2 D (D) 2 These four copolymerized units are all right.
Further, in the aforementioned ion-conducting polymer, A 1 、B 1 、C 1 D (D) 1 The copolymerization units respectively corresponding to the four copolymerization units are not necessarily copolymerization units with one structure, but also copolymerization units formed by copolymerization subunits with different structures; a is that 2 、B 2 、C 2 D (D) 2 The copolymerized units corresponding to the four copolymerized units are not necessarily copolymerized units with one structure, but copolymerized units formed by copolymerized subunits with different structures. For example, A 1 The structural formula of the copolymerization unit is as follows:，A 1 the copolymerized units may be copolymerized units of only one structure, or the copolymerized units A may be copolymerized units of +.>、/>And +.>A copolymer unit formed of a plurality of copolymer subunits, wherein Ar 1a 、Ar 1b Ar, ar 1c Etc. may be the same or different, R 1a 、R 1b R is as follows 1c Etc. may be the same or different, R 2a 、R 2b R is as follows 2c Etc. may be the same or different; b (B) 1 、C 1 、D 1 、A 2 、B 2 、C 2 D (D) 2 The seven copolymerized units are the same and are not described in detail herein.
The present application does not apply to Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 Ar, ar 8 The "ligation site on" is defined. The salt units refer to: having a structure formed by "a first anionic unit covalently linked to an ion-conducting cross-linking substance" and "a first cationic unit electrostatically bound to the first anionic unit"; or, the salt unit means: has a structure formed by "a second cationic unit covalently linked to an ion-conducting cross-link" and "a second anionic unit electrostatically bound to the second cationic unit". The amine group may be a primary amine group, a tertiary amine group, a quaternary amine group, or a cyclic amine group; positively charged ammonium groups refer to: the N atom in the amine group is positively charged by protonation. In the present application, when reference is made to "amine group" only, "amine group" means: uncharged amine groups. P (P) 1 And P 2 May be the same or different ion conducting polymers. w may be 1, 2, 3, 4, 5, 6.
According to the method, the cross-linking structure in the ion-conducting cross-linked matter is adjusted to enable the cross-linking structure to be of a structure containing amino groups or/and positively charged ammonium groups, and the ion-conducting cross-linked matter is adopted to prepare the anion-exchange membrane, so that the ion conductivity of the anion-exchange membrane can be improved, and the anion-exchange membrane has good electrochemistry; the swelling rate of the anion exchange membrane can be reduced, and the alkali stability of the anion exchange membrane can be improved, so that the anion exchange membrane has longer service life, and the application range of the anion exchange membrane is widened to a great extent.
In some embodiments, the foregoing cross-linking structure may be the case as shown in the first example, where the cross-linking structure has the formula；v(X a - ) Is an anion, v is a natural number of 1 to 4, z is a natural number of 1 to 4, and v=z;the structural formula is as follows: />. Wherein R is 13 Selected from monocyclic aromatic groups, condensed ring aromatic groups or alkyl groups; r is R 14 R is as follows 15 Are positively charged ammonium groups; r is R 16 R is as follows 17 Each independently selected from the group consisting of hydrogen atom, amine group,/->、Substituted or unsubstituted alkyl, substituted or unsubstituted aryl; wherein T is 1 T is as follows 2 Are positively charged ammonium groups, P 3 Is a third ion-conducting polymer, P 4 Is a fourth ion conducting polymer.
v(X a - ) The representation is: v X a - 。P 1 、P 2 、P 3 And P 4 May be the same or different ion conducting polymers. When "R 16 R is as follows 17 Each independently selected fromOr->"when, T 1 Or/and T 2 "can be combined with" R 14 Or/and R 15 "same," T 1 Or/and T 2 "can also be combined with" R 14 Or/and R 15 "different," the application is not limited.
The cross-linked structure in the ion-conducting cross-linked material is the cross-linked structure shown in the first example, so that the anion-exchange membrane prepared by adopting the ion-conducting cross-linked material has higher ion conductivity, lower swelling rate and higher alkali stability.
In some embodiments, in the crosslinked structure shown in the first example, R 13 Selected from phenyl, biphenyl, terphenyl, naphthyl and alkyl with the carbon number more than or equal to 2; is beneficial to further improving the ion conductivity of the anion exchange membrane and reducing the swelling rate of the anion exchange membrane. Further, R 13 Selected from alkyl groups with 2-3 carbon atoms, p-terphenyl groups or biphenyl groups; is beneficial to further improving the ion conductivity of the anion exchange membrane and reducing the swelling rate of the anion exchange membrane.
In some embodiments, in the crosslinked structure shown in the first example, the amine group is selected from at least one of a tertiary amine group and a cyclic amine group; the positively charged ammonium group is selected from at least one of quaternary ammonium groups and positively charged cyclic amine groups; is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane and further reducing the swelling rate of the anion exchange membrane.
Further, in the crosslinked structure shown in the first example, the tertiary amino group may be a dimethylamino group. Is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane and further reducing the swelling rate of the anion exchange membrane.
In the crosslinked structure shown in the first example, the quaternary ammonium group is . Cyclic amine groupsAt least one selected from the group consisting of imidazolyl, pyridyl, pyrazolyl, pyrrolidinyl, pyrrolyl, pyrimidinyl, piperidyl, indolyl, and triazinyl; the positively charged cyclic amine group is selected from at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium. Is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane.
Further, in the crosslinked structure shown in the first example, the cyclic amine group is selected from at least one of an imidazolyl group and a piperidyl alkyl group; the positively charged cyclic amine group is selected from at least one of imidazolium and piperidinium. Still further, in the crosslinked structure shown in the first example, the cyclic amine group is a piperidyl group; the positively charged cyclic amine group is piperidinium. Is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane.
In some embodiments, the cross-linked structure shown in the first example has the following structural formula:、or->The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 13 X is as follows a - Please refer to the above, and the description is omitted here. The structural formula of the cross-linked structure in the ion-conducting cross-linked substance is shown as above, which is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane and further reducing the swelling rate of the anion exchange membrane.
As an example, the first example showsThe structural formula is as follows: />、Or->。
In some embodiments, X a - At least one selected from the group consisting of a halogen ion, a bicarbonate ion, a hydroxide ion, a trifluoromethanesulfonic acid anion, a p-trifluorobenzenesulfonic acid anion, a phosphorus hexafluoride anion, and a boron tetrafluoride anion. Further, X a - Is halogen ion; for example, X a - Is chloride, iodide or bromide. In other embodiments, X a - The anions are not limited to those provided above, and may be, for example, p-toluenesulfonic acid anions or the like.
In some embodiments, the foregoing cross-linking structure may be the case as shown in the second example, where the structural formula of the cross-linking structure is as follows:or->The method comprises the steps of carrying out a first treatment on the surface of the Wherein d is more than or equal to 1, and both c and t are more than or equal to 0; r is R 18 、R 19 、R 20 、R 21 、R 22 And R is 23 Each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group; r is R 24 R is as follows 25 Each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; r is R 26 R is as follows 27 Each independently selected from the group consisting of a hydrogen atom, a group containing a carbon-carbon double bond, ">、/>Substituted or unsubstituted alkyl, substituted or unsubstituted aryl; wherein T is 3 T is as follows 4 Are each substituted or unsubstituted alkyl, P 5 P being a fifth ion-conducting polymer 6 Is a sixth ion conducting polymer.
P 1 、P 2 、P 3 、P 4 、P 5 And P 6 May be the same or different ion conducting polymers.
The cross-linked structure in the ion-conducting cross-linked material is the cross-linked structure shown in the second example, so that the anion-exchange membrane prepared by adopting the ion-conducting cross-linked material has higher ion conductivity, lower swelling rate and higher alkali stability.
In some embodiments, in the crosslinked structure shown in the second example, c and t are both > 0.
In some embodiments, in the crosslinked structure shown in the second example, R 18 、R 19 、R 20 、R 21 、R 22 And R is 23 Are all hydrogen atoms.
In some embodiments, in the crosslinked structure shown in the second example, R 24 R is as follows 25 Each independently selected from substituted or unsubstituted C 1 ~C 3 Is a hydrocarbon group.
In some embodiments, in the crosslinked structure shown in the second example, R 26 R is as follows 27 Each independently selected from the group consisting of hydrogen atoms, and groups containing carbon-carbon double bonds. Further, R 26 R is as follows 27 Each independently selected from hydrogen atoms or。
In some embodiments, the cross-linked structure shown in the second example has the following structural formula:or (b)The method comprises the steps of carrying out a first treatment on the surface of the Wherein d is more than or equal to 1. The structural formula of the cross-linked structure in the ion-conducting cross-linked material is shown in the specification, which is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane and further reducing the swelling rate of the anion exchange membrane.
In some embodiments, ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 Ar, ar 8 Each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted o-terphenyl, substituted or unsubstituted p-tetrabiphenyl, substituted or unsubstituted pentabiphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diethylfluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl ether, substituted or unsubstituted diphenyl sulfide, substituted or unsubstituted diphenyl sulfone, and substituted or unsubstituted diphenyl sulfoxide.
It will be appreciated that Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 Ar, ar 8 May be the same or different. For example, ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 Ar, ar 8 May be selected from the following structures:、/>or->。
In some embodiments, R 1 R is as follows 7 Each independently selected from halogen substituted or unsubstituted alkyl, halogen substituted or unsubstituted aryl; further, R 1 R is as follows 7 All are phenyl groups.
In some embodiments, R 2 R is as follows 8 Each independently selected from halogen substituted or unsubstituted alkyl, halogen substituted or unsubstituted aryl; further, R 2 R is as follows 8 Each independently selected from fluorine atom substituted alkyl or fluorine atom substituted arylThe method comprises the steps of carrying out a first treatment on the surface of the Further, R 2 R is as follows 8 Each independently selected from fluorine atom substituted C 1 ~C 3 An alkyl group or a fluorine atom-substituted aryl group.
In some embodiments, R 2 R is as follows 8 Are trifluoromethyl; is beneficial to increasing the hydrophilicity of the ion-conducting cross-linked matter.
In some embodiments, R a R is as follows b Is of the structure of；R 3 R is as follows 4 Each independently selected from the group consisting of substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, structures containing salt units, and hydrogen atoms; x is X 1 - Is anionic.
In some embodiments, R 3 R is as follows 4 All being substituted or unsubstituted C 1 ~C 3 Is a hydrocarbon group. Further, R 3 R is as follows 4 Are all methyl groups.
In some embodiments, X 1 - X is as follows 2 - Each independently selected from at least one of a halogen ion, a bicarbonate ion, a hydroxide ion, a trifluoromethanesulfonic acid anion, a p-trifluorobenzenesulfonic acid anion, a phosphorus hexafluoride anion, and a boron tetrafluoride anion. Further, X 1 - X is as follows 2 - Each independently is a halide ion; for example, X 1 - X is as follows 2 - Each independently is chloride, iodide or bromide. In other embodiments, X 1 - X is as follows 2 - The anions are not limited to those provided above, and may be, for example, p-toluenesulfonic acid anions or the like.
In some embodiments, R f R is as follows h Each independently selected from C 1 ~C 3 C substituted by alkyl or halogen atoms 1 ~C 3 Is a hydrocarbon group.
In some embodiments, R 5 R is as follows 11 Each independently selected from C 1 ~C 3 Alkyl, halogen atoms of (C)Substituted C 1 ~C 3 Is an alkyl group containingStructure or contain->Is a structure of (a).
In some embodiments, x is 0 and s > 0.
In some embodiments, s is a natural number of 1-3; for example, s may be 1, 2 or 3.
In some embodiments, y is 0 and q > 0.
In some embodiments, q is a natural number from 1 to 3; for example, q may be 1, 2 or 3.
In some embodiments, x and y are both 0, and s and q are both natural numbers from 1 to 3.
In some embodiments, j is 0 and k > 0.
In some embodiments, k is a natural number of 1-3; for example, k may be 1, 2 or 3.
In some embodiments, u is 0 and a > 0.
In some embodiments, a is a natural number of 1 to 3; for example, a may be 1, 2 or 3.
In some embodiments, j and u are both 0, and k and a are both natural numbers 1-3.
In some embodiments, the ionomer has the formula:
、、/>、、/>、、. The structural formula of the ion-conducting cross-linked compound is shown in the specification, so that the anion-exchange membrane prepared by the ion-conducting cross-linked compound has higher ion conductivity, lower swelling rate and higher alkali stability.
In some embodiments, 25% of the ion-conducting crosslinks are ≡m 1 /(m 1 +n 1 +p 1 +p 3 )≥0，99.99%≥n 1 /(m 1 +n 1 +p 1 +p 3 )≥60%，25%≥(p 1 +p 3 )/(m 1 +n 1 +p 1 +p 3 )≥0.01%，25%≥m 2 /(m 2 +n 2 +p 2 +p 4 )≥0，99.99%≥n 2 /(m 2 +n 2 +p 2 +p 4 )≥60%，25%≥(p 2 +p 4 )/(m 2 +n 2 +p 2 +p 4 )≥0.01%。
In some embodiments, the number average molecular weight of the ion-conducting cross-link is 10000Da to 1000000Da.
The present application also provides a method for preparing a first example of an ion-conducting cross-link, the method for preparing the first example comprising: and (3) carrying out a crosslinking reaction on the system containing the ion-conducting polymer and the crosslinking agent. The cross-linking agent is a cross-linking agent containing amino groups. The structure of the ion conducting polymer (formula I) is as follows:the method comprises the steps of carrying out a first treatment on the surface of the Wherein m is greater than or equal to 0, n is greater than 0, p is greater than 0, and x 1 0 or 1, s 1 Not less than 0 and x 1 And s 1 Not simultaneously 0; ar (Ar) 1a 、Ar 2a Ar, ar 3a Each independently selected from substituted or unsubstituted aryl; r is R 1a R is as follows 6a Each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; r is R 2a Is a group containing fluorine atoms；R 5a A group selected from the group consisting of a structure containing a salt unit, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a halogen atom; r is R 30 Is a halogen atom; r is R a1 The structural formula is as follows: />Or->；R 3a R is as follows 4a Each independently selected from the group consisting of substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, structures containing salt units, and hydrogen atoms; x is X 1a - X is as follows 2a - Are anions; w (w) 1 Is a natural number of 1 to 6.
The ion conduction cross-linked matter prepared by the preparation method of the ion conduction cross-linked matter provided by the application can not only improve the ion conductivity of the anion exchange membrane prepared by the ion conduction cross-linked matter, so that the anion exchange membrane has better electrochemistry; the swelling rate of the anion exchange membrane can be reduced, and the alkali stability of the anion exchange membrane can be improved, so that the anion exchange membrane has longer service life, and the application range of the anion exchange membrane is widened to a great extent.
The "ratio of m, n and p" in formula I to "m" in the formula of the ion-conducting cross-link 1 、n 1 (p) 1 +p 3 ) The ratio of "" or "" m 2 、n 2 (p) 2 +p 4 ) Is identical to the ratio of (1); ar in formula I 1a Ar in structural formula of ion-conducting cross-linked matter 1 Or Ar 4 "in accordance with, ar in formula I 2a Ar in structural formula of ion-conducting cross-linked matter 2 Or Ar 5 "in accordance with, ar in formula I 3a Ar in structural formula of ion-conducting cross-linked matter 3 Or Ar 6 "consistent; r in formula I 1a R in structural formula of ion-conductive cross-linked matter 1 Or R is 7 "in accordance with, R in formula I 2a R in structural formula of ion-conductive cross-linked matter 2 Or R is 8 "in agreement with each other,r in formula I 6a R in structural formula of ion-conductive cross-linked matter 6 Or R is 12 "in accordance with, R in formula I 5a R in structural formula of ion-conductive cross-linked matter 5 R is as follows 11 Each independently selected from the group consisting of a salt unit-containing structure, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a halogen atom-containing group ", R in formula I 3a R in structural formula of ion-conductive cross-linked matter 3 "in accordance with, R in formula I 4a R in structural formula of ion-conductive cross-linked matter 4 "in accordance with, X in formula I 1a - X in structural formula of ion-conductive cross-linked matter 1 - "in accordance with, X in formula I 2a - X in structural formula of ion-conductive cross-linked matter 2 - "consistent, w in formula I 1 Consistent with "w" in the structural formula of the ion-conducting cross-linker, no further description is provided herein.
In some embodiments, R 5a Is halogen substituted or unsubstituted alkyl. Further, R 5a Selected from C 1 ~C 3 C substituted by alkyl groups or halogen atoms 1 ~C 3 Is a hydrocarbon group.
Illustratively, R is 5a Can be methyl, R 5a Can be a chlorine atom-substituted methyl group, an iodine atom-substituted methyl group, a fluorine atom-substituted methyl group, or the like.
In some embodiments, R 30 Selected from chlorine atoms, iodine atoms or bromine atoms. In other embodiments, R 30 And may also be selected from fluorine atoms.
In some embodiments, the crosslinking agent includes at least one of a polyamine-based crosslinking agent and an olefinic crosslinking agent. The ion-conducting polymer may be allowed to undergo a cross-linking reaction to form an ion-conducting cross-link.
In the present application, the polyamine-based crosslinking agent means a crosslinking agent containing at least two amine groups, and the olefin-based crosslinking agent means a crosslinking agent containing a carbon-carbon double bond.
In some embodiments, the aforementioned crosslinking agents may be the first example (i.e., polyamine-based cross-linkingCo-agent), in a first example, the cross-linking agent has the following structural formula:the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 31 Selected from monocyclic aromatic groups, condensed ring aromatic groups or alkyl groups; r is R 32 R is as follows 33 All have structures containing amino groups; r is R 34 R is as follows 35 Each independently selected from the group consisting of a hydrogen atom, a structure containing an amine group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group.
The cross-linking agent used in the process of preparing the ion-conducting cross-linked material is the cross-linking agent shown in the first example, so that the anion exchange membrane prepared by adopting the ion-conducting cross-linked material has higher ion conductivity, lower swelling rate and higher alkali stability.
In some embodiments, in the crosslinker shown in the first example, R 31 Selected from phenyl, biphenyl, terphenyl, naphthyl and alkyl with the carbon number more than or equal to 2; is beneficial to further improving the ion conductivity of the anion exchange membrane and reducing the swelling rate of the anion exchange membrane. Further, R 31 Selected from alkyl groups with 2-3 carbon atoms, p-terphenyl groups or biphenyl groups; is beneficial to further improving the ion conductivity of the anion exchange membrane and reducing the swelling rate of the anion exchange membrane.
In some embodiments, in the crosslinking agent shown in the first example, the amine group is selected from at least one of a tertiary amino group and a cyclic amino group; is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane and further reducing the swelling rate of the anion exchange membrane.
Further, the tertiary amino group may be a dimethylamino group. Is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane and further reducing the swelling rate of the anion exchange membrane.
Further, the cyclic amine group is selected from at least one of imidazolyl, pyridyl, pyrazolyl, pyrrolidinyl, pyrrolyl, pyrimidinyl, piperidyl, indolyl, and triazinyl. Is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane.
Still further, in the crosslinking agent shown in the first example, the cyclic amine group is selected from at least one of an imidazolyl group and a piperidyl alkyl group. Still further, in the crosslinking agent shown in the first example, the cyclic amine group is a piperidyl group. Is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane.
In some embodiments, the cross-linking agent shown in the first example has the formula:、or->The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 31 Please refer to the above, and the description is omitted here. The structural formula of the cross-linking agent used in the process of preparing the ion-conducting cross-linked matter is shown in the specification, which is beneficial to further improving the ion conductivity and alkali stability of the anion exchange membrane and further reducing the swelling rate of the anion exchange membrane.
Illustratively, the structural formula of the crosslinker shown in the first example is as follows:、or->。
In some embodiments, the foregoing crosslinking agent may be the case as shown in the second example (i.e., an olefinic crosslinking agent), where the structural formula of the crosslinking agent is as follows:the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 36 Is a group containing a carbon-carbon double bond; r is R 37 R is as follows 38 Each independently selected from the group consisting of a hydrogen atom, a group containing a carbon-carbon double bond, a substituted or unsubstituted alkyl groupSubstituted or unsubstituted aryl.
The cross-linking agent used in the process of preparing the ion-conducting cross-linked matter is the cross-linking agent shown in the second example, so that the anion exchange membrane prepared by adopting the ion-conducting cross-linked matter has higher ion conductivity, lower swelling rate and higher alkali stability, and the application range of the anion exchange membrane is further widened.
In some embodiments, in the crosslinking agent shown in the second example, R 37 R is as follows 38 Each independently selected from a hydrogen atom or a group containing a carbon-carbon double bond. Further, R 37 R is as follows 38 Each independently selected from hydrogen atoms or。
Further, the olefinic crosslinking agent may include at least one of diallylamine, triallylamine, 3-buten-1-amine, N-dimethyl-4-alkenylaniline, and 4-vinylaniline.
Illustratively, the structural formula of the olefinic crosslinking agent is as follows:。
in some embodiments, the method of making an ion-conducting cross-link includes: the system comprising the ion-conducting polymer provided previously and the first solvent is subjected to a crosslinking reaction in the presence of a crosslinking agent.
As an example, the first solvent includes at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone. The first solvent is selected from the substances, so that the ion-conducting polymer and the crosslinking agent can be well dissolved and dispersed.
In some embodiments, the time of the crosslinking reaction is 12-72 hours, and the temperature of the crosslinking reaction is 20-150 ℃. The conditions for the crosslinking reaction can be such that the crosslinking reaction proceeds well.
In some embodiments, the method of making an ion-conducting cross-link further comprises: after the crosslinking reaction, adding the system after the crosslinking reaction into a second solvent, and taking out the precipitated solid phase to obtain the ion conduction crosslinked product. When the ion-conducting crosslinked material is used to prepare the anion-exchange membrane, the ion-conducting crosslinked material in a solid phase is dissolved in dimethyl sulfoxide, and then the anion-exchange membrane is prepared.
As an example, the second solvent includes at least one of tetrahydrofuran, ethyl acetate, petroleum ether, toluene, chlorobenzene, dichloromethane, dichloroethane, and chloroform. The second solvent is selected from the solvents, so that the prepared ion conduction cross-linked matter can be separated out in the second solvent, and the purification of the ion conduction cross-linked matter is facilitated.
For ion conducting polymers of formula I, the present application illustratively provides a method of preparing such ion conducting polymers. The method for preparing the ion conducting polymer of the formula I comprises the following steps: copolymerizing the first component and the second component in the presence of a catalyst; and then adding a third component into the system after the copolymerization reaction to carry out salt forming reaction. The catalyst comprises at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, concentrated sulfuric acid, p-toluenesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, perfluoropropionic acid, heptafluorobutyric acid and phosphotungstic acid. The first component is a substituted or unsubstituted aromatic compound. The second component includes a first monomer and a second monomer, or the second component includes a first monomer, a second monomer, and a third monomer. The structural formula of the first monomer is as follows: The method comprises the steps of carrying out a first treatment on the surface of the The structural formula of the second monomer is as follows: />The method comprises the steps of carrying out a first treatment on the surface of the The structural formula of the third monomer is as follows: />The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is 1 0 or 1, s 1 Not less than 0 and x 1 And s 1 Not simultaneously 0; r is R 1a R is as follows 6a Each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; r is R 2a Is a group containing a fluorine atom; r is R 5a A group selected from the group consisting of a structure containing a salt unit, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a halogen atom; r is R 30 Is a halogen atom; r is R e The structural formula is as follows:or->；R 3a Selected from the group consisting of substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, structures containing salt units, and hydrogen atoms; the third component comprises a first substance or/and a second substance, the first substance has a structural formula of R 4a -R 39 The structural formula of the second substance is->，R 4a Selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted aryl, R 39 、R 9 R is as follows 10 Each independently selected from halogen atoms, carbonate groups or sulfate groups, w 1 Is a natural number of 1 to 6.
Preparation of the first, second, third and R in the third component employed in the ion-conducting polymer of formula I 1a 、R 2a 、R 3a 、R 4a 、R 5a 、R 6a 、x 1 、s 1 、w 1 R is as follows 30 Respectively with R in the ion-conducting polymer (i.e. formula I) provided above 1a 、R 2a 、R 3a 、R 4a 、R 5a 、R 6a 、x 1 、s 1 、w 1 R is as follows 30 Consistent, no further description is provided herein.
The first component used in preparing the ion-conducting polymer of formula I is according to Ar in the ion-conducting polymer described previously (i.e., formula I) 1 、Ar 2 Ar, ar 3 Corresponding selections are made, for example, when "ion-conducting polymer has Ar alone 2 Ar, ar 3 "and" Ar 2 Ar, ar 3 Are all opposite toWhen the terphenyl group is, the first component is p-terphenyl; when "having Ar only in ion-conducting polymer 2 Ar, ar 3 "and" Ar 2 Is biphenyl, ar 3 In the case of p-terphenyl ", the first component is selected from biphenyl and p-terphenyl.
In the second component used in preparing the ion-conducting polymer shown in formula I, the molar ratio of the first monomer to the second monomer to the third monomer is n:p:m, which is identical to n:p:m in the ion-conducting polymer (i.e. formula I) provided above, and will not be described here again.
When R in formula I a1 Is of the structure ofWhen R in the first monomer e Is selected as +.>And the third component selects the first substance; when R in formula I a1 Is of the formula->When R in the first monomer e Is selected as +.>And the third component selects the second substance.
In some embodiments, the method of making an ion conducting polymer (i.e., formula i) includes: in the presence of a catalyst, a system comprising a first component, a second component and a third solvent is subjected to a copolymerization reaction. As an example, the third solvent includes at least one of dichloromethane, chloroform, nitrobenzene, 1, 2-dichloroethane, carbon disulfide, petroleum ether, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide. The third solvent is selected from the substances, so that the first component, the second component and the catalyst can be well dissolved and dispersed.
In some embodiments, the copolymerization is performed at-10 ℃ -100 ℃ (e.g., under ice bath conditions); further, the copolymerization is carried out at the temperature of-10 ℃ to 70 ℃, which is favorable for better carrying out the copolymerization.
In some embodiments, the method of making an ion conducting polymer (i.e., formula i) includes: and adding a catalyst into a system containing the first component, the second component and the third solvent at the temperature of-10 ℃ to 100 ℃ and then carrying out copolymerization reaction. Further, the time of the copolymerization reaction is 5-24 hours. Under the above copolymerization conditions, the copolymerization reaction can be made to proceed well.
In some embodiments, the molar ratio of catalyst to first component is (2-5): 1; is beneficial to improving the efficiency of the copolymerization reaction.
In some embodiments, the molar ratio of the first component to the second component is 1 (0.8-1.2); is beneficial to improving the efficiency of the copolymerization reaction.
In some embodiments, R in the first and second substances 39 、R 9 R is as follows 10 Each independently selected from a bromine atom, an iodine atom, a chlorine atom, a carbonate group, or a sulfate group. As an example, the first substance is selected from at least one of methyl iodide, dimethyl carbonate, dimethyl sulfate, methyl bromide, methyl chloride, ethyl bromide, ethyl chloride, and ethyl iodide.
In some embodiments, the salt forming reaction is carried out at a temperature of 0-150 ℃ for 12-72 hours; under the above copolymerization conditions, the salt formation reaction can be made to proceed well.
In some embodiments, the molar ratio of the third component to the first monomer is greater than or equal to 1:1; further, the molar ratio of the third component to the first monomer is more than or equal to 1:2; is favorable for better salt forming reaction and improves the efficiency of the salt forming reaction.
In some embodiments, a method of making an ion conducting polymer includes: slowly dripping the system after the copolymerization into a fourth solvent before the salification reaction, and filtering to obtain a first solid; then immersing the first solid in an alkaline solution, and filtering to obtain a second solid; mixing the dried second solid with a fifth solvent to obtain a mixed system; and adding a third component into the mixed system to carry out salt forming reaction. Wherein the fourth solvent comprises at least one of ethanol, methanol, water, ethyl acetate and tetrahydrofuran; the alkaline solution comprises at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate; the fifth solvent includes at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
The present application also provides a method for preparing a second example of an ion-conducting cross-link, the method for preparing the second example comprising: carrying out a crosslinking reaction on a system containing a first polymer and a crosslinking agent; then adding a salifying substance into the system after the crosslinking reaction to carry out salifying reaction. Wherein the cross-linking agent is a cross-linking agent containing an amine group; the structural formula (formula II) of the first polymer is as follows:
。
the crosslinking agent and the salt-forming substance used in the production method in the second example are respectively identical to those used in the production method in the aforementioned first example and the third component used in the production of formula i; the crosslinking reaction conditions in the production method in the second example are identical to those in the aforementioned first example; ar in formula II 1a 、Ar 2a 、Ar 3a 、R 1a 、R 2a 、R 5a 、R 6a 、R 30 、m、n、p、x 1 S 1 Ar "in the formula I described above 1a 、Ar 2a 、Ar 3a 、R 1a 、R 2a 、R 5a 、R 6a 、R 30 、m、n、p、x 1 S 1 "consistent" is not repeated here.
In the formula II, R c The structural formula is as follows:or->The method comprises the steps of carrying out a first treatment on the surface of the In the formula II, R c R in (a) 3a With R in formula I 3a Consistent, no further description is provided herein.
It is noted that when R in formula II c Is of the structure ofWhen the salt forming substance is selected from the first substances; when R in formula II c Is of the formula->In this case, the salt-forming substance is selected from the aforementioned second substances. />
Wherein the preparation step of the first polymer shown in the formula II comprises the following steps: the first component and the second component are subjected to a copolymerization reaction in the presence of a catalyst. The copolymerization conditions, catalyst selection, first component selection and second component selection involved in the preparation step of the first polymer of formula II are identical to those involved in the preparation step of the ion-conducting polymer of formula I, and are not described in detail herein.
The application provides an anion exchange membrane, wherein the material of the anion exchange membrane comprises an ion conduction cross-linked matter; or, the anion exchange membrane comprises a porous supporting layer and a filler filled in the pores of the porous supporting layer, wherein the filler comprises inorganic hydrophilic particles and ion conduction cross-linking substances; or, the anion exchange membrane comprises a porous supporting layer and a filler filled in the pores of the porous supporting layer, wherein the filler comprises an ion conduction cross-link; alternatively, the anion exchange membrane comprises inorganic hydrophilic particles and ion-conducting crosslinks. The ion-conducting crosslinked material is the ion-conducting crosslinked material provided by the method for preparing the ion-conducting crosslinked material.
The anion exchange membrane provided by the application has higher ion conductivity, lower swelling rate and higher alkali stability, namely the anion exchange membrane has better electrochemical performance and longer service life, and is beneficial to widening the application range of the anion exchange membrane to a great extent.
In some embodiments, the porous support layer comprises at least one of polypropylene, polyethylene, polysulfone, polyphenylene sulfide, polyamide, polyethersulfone, polyphenylsulfone, polyethylene terephthalate, polyetheretherketone, sulfonated polyetheretherketone, expanded polytetrafluoroethylene, chlorotrifluoroethylene, a copolymer of ethylene and tetrafluoroethylene, a copolymer of ethylene and chlorotrifluoroethylene, polyimide, polyetherimide, and meta-aramid; the porosity of the porous supporting layer is 40% -90%; the thickness of the porous support layer is 1-60 μm.
In some embodiments, the inorganic hydrophilic particles comprise at least one of zirconia, barium sulfate, hydrotalcite, titanium dioxide, zinc carbonate, magnesium hydroxide, nickel hydroxide, and hydrotalcite materials; the particle size of the inorganic hydrophilic particles is 1 nm-1 mu m; the inorganic hydrophilic particles account for less than or equal to 60 percent of the mass fraction of the ion conduction system.
The application provides an application of the anion exchange membrane provided above in preparing an electrolyzed water device, an electrodialysis device, a fuel cell or an electrochemical energy storage device; the electrochemical energy storage device comprises a flow battery.
Example 1
The embodiment provides a preparation method of an anion exchange membrane, which comprises the following steps:
(1) 2.3g of p-terphenyl, 1.07g of N-methyl-4-piperidone, 0.064g of dichloroacetone and 7mL of dichloromethane are added into a reaction bottle and mixed to obtain a mixed system; then the reaction bottle is transferred into an ice bath environment, 7mL of trifluoromethanesulfonic acid is slowly added into the reaction bottle, and the reaction is carried out for 24 hours in the ice bath environment, so as to obtain a viscous solution. Slowly dripping into tetrahydrofuran solution to separate out solid; then the precipitated solid is soaked in 1M aqueous solution of potassium carbonate, stirred for 8 hours, filtered and dried to obtain the initial polymer.
Wherein the structural formula of the initial polymer is as follows:
。
(2) 1g of the initial polymer obtained in the step (1) is placed in a reaction bottle, then 20mL of dimethyl sulfoxide is added into the reaction bottle, then 1mL of methyl iodide is added into the reaction bottle, the reaction is carried out for 12 hours at 25 ℃, the obtained system is dripped into ethyl acetate, solids are separated out, and then the solids are dried at 60 ℃ to obtain the ion-conducting polymer.
Wherein the ion conducting polymer has the following structural formula:
。
(3) 1g of the ion-conducting polymer obtained in the step (2) was dissolved in 10mL of dimethyl sulfoxide, then 30mg of tetramethyl ethylenediamine was added to the solution, the reaction was carried out at 100℃for 24 hours, the obtained system was dropped into ethyl acetate to precipitate a solid, and the solid was dried at 60℃to obtain an ion-conducting crosslinked material.
Wherein the ionic conduction cross-linked substance has the following structural formula:
。
(4) 1g of the ion-conducting crosslinked material obtained in the step (3) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Casting the casting solution on a glass substrate, drying at 80 ℃ for 12 hours to form a film-shaped substance, then soaking the film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and then demolding to obtain the anion exchange membrane.
Example 2
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: 30mg of tetramethyl ethylenediamine in step (3) of example 1 was replaced with 61.5mg of 4,4' -trimethylenebis (1-methylpiperidine), and the ionic conduction cross-linked product according to this example had the following structural formula:
。
example 3
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: 30mg of tetramethyl ethylenediamine in step (3) of example 1 was replaced with 95.6mg of 4,4 '-bis (2, 4, 5-trimethyl-1H-imidazole) -1,1' -biphenol (as a crosslinking agent).
Wherein, the structural formula of the 4,4 '-bis (2, 4, 5-trimethyl-1H-imidazole) -1,1' -biphenyl is as follows:
。
The preparation method of the 4,4 '-bis (2, 4, 5-trimethyl-1H-imidazole) -1,1' -biphenyl comprises the following steps: trimethylimidazole (CAS number: 822-90-2,3 eq) was added to a dry 100mL Schleck flask containing 10mL anhydrous DMF, and a clean stirrer was added with 20mg of water-removing molecular sieve, 4' -dibromobiphenyl (CAS number: 92-86-4,3.12g,1 eq), thiophene-2-cuprous formate (CAS number: 68986-76-5,0.4 eq), 4, 7-dimethoxy-1, 10-phenanthroline (CAS number: 92149-07-0,0.4 eq) and potassium tert-butoxide (6 eq) were added in portions with stirring at room temperature, and after the addition, three nitrogen displacement treatments were performed, and placed in an oil bath, slowly warmed to 160 ℃, and after the reaction for 18H, purified by column chromatography (eluent was methanol and dichloromethane in a volume ratio of 1:12) to give 4,4' -bis (2, 4, 5-trimethyl-1H-imidazole) -1,1' -biphenyl.
The structural formula of the ion-conducting crosslinked material corresponding to this example is as follows:
。
example 4
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: 30mg of tetramethyl ethylenediamine in step (3) of example 1 was replaced with 25.1mg of diallylamine.
The structural formula of the ion-conducting crosslinked material corresponding to this example is as follows:
。
Example 5
The embodiment provides a preparation method of an anion exchange membrane, which comprises the following steps:
(1) 1.54g of biphenyl, 1.07g of N-methyl-4-piperidone, 0.108g of dibromoacetone and 7mL of methylene dichloride are added into a reaction bottle and mixed to obtain a mixed system; then the reaction bottle is transferred into an ice bath environment, 7mL of trifluoromethanesulfonic acid is slowly added into the reaction bottle, and the reaction is carried out for 24 hours in the ice bath environment, so as to obtain a viscous solution. Slowly dripping into tetrahydrofuran solution to separate out solid; then the precipitated solid is soaked in 1M aqueous solution of potassium carbonate, stirred for 8 hours, filtered and dried to obtain the initial polymer.
Wherein the structural formula of the initial polymer is as follows:
。
(2) 1g of the initial polymer obtained in the step (1) is placed in a reaction bottle, then 20mL of dimethyl sulfoxide is added into the reaction bottle, then 1mL of methyl iodide is added into the reaction bottle, the reaction is carried out for 12 hours at 25 ℃, the obtained system is dripped into ethyl acetate, solids are separated out, and then the solids are dried at 60 ℃ to obtain the ion-conducting polymer.
Wherein the ion conducting polymer has the following structural formula:
。
(3) 1g of the ion-conducting polymer obtained in the step (2) was dissolved in 10mL of dimethyl sulfoxide, then 30mg of tetramethyl ethylenediamine was added to the solution, the reaction was carried out at 100℃for 24 hours, the obtained system was dropped into ethyl acetate to precipitate a solid, and the solid was dried at 60℃to obtain an ion-conducting crosslinked material.
Wherein the ionic conduction cross-linked substance has the following structural formula:
。
(4) 1g of the ion-conducting crosslinked material obtained in the step (3) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Casting the casting solution on a glass substrate, drying at 80 ℃ for 12 hours to form a film-shaped substance, then soaking the film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and then demolding to obtain the anion exchange membrane.
Example 6
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: 2.3g of p-terphenyl from example 1 was replaced by 2.3g of m-terphenyl and 0.064g of dichloroacetone was replaced by 0.108g of dibromoacetone; the structural formula of the initial polymer corresponding to this example is as follows:
。
the structural formula of the ion conducting polymer corresponding to this example is as follows:
。
the structural formula of the ion-conducting crosslinked material corresponding to this example is as follows:
。
example 7
The embodiment provides a preparation method of an anion exchange membrane, which comprises the following steps:
(1) 2.3g of p-terphenyl, 96.25mg of N-methyl-4-piperidone, 0.174g of trifluoroacetophenone, 0.108g of dibromoacetone and 7mL of dichloromethane are added into a reaction bottle and mixed to obtain a mixed system; then the reaction bottle is transferred into an ice bath environment, 7mL of trifluoromethanesulfonic acid is slowly added into the reaction bottle, and the reaction is carried out for 24 hours in the ice bath environment, so as to obtain a viscous solution. Slowly dripping into tetrahydrofuran solution to separate out solid; then the precipitated solid is soaked in 1M aqueous solution of potassium carbonate, stirred for 8 hours, filtered and dried to obtain the initial polymer.
Wherein the structural formula of the initial polymer is as follows:
。
(2) 1g of the initial polymer obtained in the step (1) is placed in a reaction bottle, then 20mL of dimethyl sulfoxide is added into the reaction bottle, then 1mL of methyl iodide is added into the reaction bottle, the reaction is carried out for 12 hours at 25 ℃, the obtained system is dripped into ethyl acetate, solids are separated out, and then the solids are dried at 60 ℃ to obtain the ion-conducting polymer.
Wherein the ion conducting polymer has the following structural formula:
。
(3) 1g of the ion-conducting polymer obtained in the step (2) was dissolved in 10mL of dimethyl sulfoxide, then 30mg of tetramethyl ethylenediamine was added to the solution, the reaction was carried out at 100℃for 24 hours, the obtained system was dropped into ethyl acetate to precipitate a solid, and the solid was dried at 60℃to obtain an ion-conducting crosslinked material.
Wherein the ionic conduction cross-linked substance has the following structural formula:
。
(4) 1g of the ion-conducting crosslinked material obtained in the step (3) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Casting the casting solution on a glass substrate, drying at 80 ℃ for 12 hours to form a film-shaped substance, then soaking the film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and then demolding to obtain the anion exchange membrane.
Example 8
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: the difference of the step (4); in this embodiment, step (4) is as follows:
1g of the ion-conducting crosslinked material obtained in the step (3) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Flatly paving a swelling polytetrafluoroethylene film with the thickness of 10 mu M and the porosity of 70% on a glass substrate, filling the prepared casting film liquid into pores of the swelling polytetrafluoroethylene film in a coating mode, drying at 80 ℃ for 12 hours to form a film-shaped substance with the filler in the pores of the swelling polytetrafluoroethylene film, soaking the dried film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and demolding to obtain the anion exchange film.
Example 9
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: the difference of the step (4); in this embodiment, step (4) is as follows:
1g of the ion-conductive crosslinked material obtained in the step (4) and 0.1g of zirconia powder having an average particle diameter of 30 μm were dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Flatly paving a swelling polytetrafluoroethylene film with the thickness of 10 mu M and the porosity of 70% on a glass substrate, filling the prepared casting film liquid into pores of the swelling polytetrafluoroethylene film in a coating mode, drying at 80 ℃ for 12 hours to form a film-shaped substance with the filler in the pores of the swelling polytetrafluoroethylene film, soaking the dried film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and demolding to obtain the anion exchange film.
Comparative example 1
The comparative example provides a method for preparing an anion exchange membrane, comprising the following steps:
(1) 2.3g of terphenyl, 1.13g of N-methyl-4-piperidone and 7mL of methylene dichloride are added into a reaction bottle and mixed to obtain a mixed system; then the reaction bottle is transferred into an ice bath environment, 7mL of trifluoromethanesulfonic acid is slowly added into the reaction bottle, and the reaction is carried out for 24 hours in the ice bath environment, so as to obtain a viscous solution. Slowly dripping tetrahydrofuran solution into the viscous solution to precipitate solid to obtain initial polymer.
Wherein the structural formula of the initial polymer is as follows:
。
(2) Soaking the initial polymer obtained in the step (1) in 1M potassium carbonate aqueous solution, stirring for 8 hours, filtering and drying, taking 1g of dried solid in a reaction bottle, adding 20mL of dimethyl sulfoxide and 1mL of methyl iodide into the reaction bottle, reacting at 25 ℃ for 12 hours, dripping the reacted system into ethyl acetate to obtain a solid product, and drying at 60 ℃ to obtain the ion-conducting polymer.
Wherein the ion conducting polymer has the following structural formula:
。
(3) 1g of the ion-conducting polymer obtained in the step (2) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Casting the casting solution on a glass substrate, drying at 80 ℃ for 12 hours to form a film-shaped substance, then soaking the film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and then demolding to obtain the anion exchange membrane.
Comparative example 2
(1) 2.3g of terphenyl, 1.07g of N-methyl-4-piperidone, 0.067g of dichloroacetone and 7mL of methylene dichloride are added into a reaction bottle and mixed to obtain a mixed system; then the reaction bottle is transferred into an ice bath environment, 7mL of trifluoromethanesulfonic acid is slowly added into the reaction bottle, and the reaction is carried out for 24 hours in the ice bath environment, so as to obtain a viscous solution. Slowly dripping tetrahydrofuran solution into the viscous solution to precipitate solid to obtain initial polymer.
Wherein the structural formula of the initial polymer is as follows:
。
(2) Soaking the initial polymer obtained in the step (1) in 1M potassium carbonate aqueous solution, stirring for 8 hours, filtering and drying, taking 1g of dried solid in a reaction bottle, adding 20mL of dimethyl sulfoxide and 1mL of methyl iodide into the reaction bottle, reacting at 25 ℃ for 12 hours, dripping the reacted system into ethyl acetate to obtain a solid product, and drying at 60 ℃ to obtain the ion-conducting polymer.
Wherein the ion conducting polymer has the following structural formula:
。
(3) 1g of the ion-conducting polymer obtained in the step (2) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Casting the casting solution on a glass substrate, drying at 80 ℃ for 12 hours to form a film-shaped substance, then soaking the film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and then demolding to obtain the anion exchange membrane.
Experimental example 1
The ion-conducting polymer obtained in the step (2) of example 1, the ion-conducting crosslinked material obtained in the step (3) of example 2, the 4 '-bis (2, 4, 5-trimethyl-1H-imidazole) -1,1' -biphenyl of example 3, the ion-conducting crosslinked material obtained in the step (3) of example 4, the ion-conducting polymer obtained in the step (2) of example 5, the ion-conducting polymer obtained in the step (2) of example 6, the ion-conducting polymer obtained in the step (2) of example 7 and the ion-conducting polymer obtained in the step (2) of comparative example 1 were subjected to structural characterization, and nuclear magnetic hydrogen spectra are shown in FIGS. 1 to 9.
As can be seen from fig. 1, the nuclear magnetic hydrogen spectrum of the ion conducting polymer prepared in step (2) of example 1 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak with the displacement of 7.45-7.77ppm corresponds to the signal of H on the aromatic ring, the peak with the displacement of 4.67ppm corresponds to the signal of methylene on dichloroacetone, the peak with the displacement of 3.35ppm corresponds to the signal of methylene on N (overlapping with the water peak), the peak with the displacement of 3.13ppm corresponds to the signal of methyl on N, and the peak with the displacement of 2.87ppm corresponds to the signal of H on the piperidine ring of methylene not connected with N.
As can be seen from fig. 2, the nuclear magnetic hydrogen spectrum of the ion-conducting cross-linked product prepared in step (3) of example 1 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the ratio of the signal intensity of the methylene group of chlorine corresponding to the shift of 4.66ppm to the signal intensity of the aromatic ring corresponding to the shift of 7.44-7.78ppm is decreased from 1:32.52 in FIG. 1 to 1 in FIG. 2: 37.29, indicating that step (3) of example 1 was subjected to the corresponding crosslinking reaction.
As can be seen from fig. 3, the nuclear magnetic hydrogen spectrum of the ion-conducting cross-linked product prepared in step (3) of example 2 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the ratio of the signal intensity of the methylene group of chlorine corresponding to the shift of 4.66ppm to the signal intensity of the aromatic ring corresponding to the shift of 7.47-7.75ppm is decreased from 1:32.52 in FIG. 1 to 1 in FIG. 3: 39.23, it is shown that step (3) of example 2 undergoes the corresponding crosslinking reaction.
As can be seen from fig. 4, the nuclear magnetic hydrogen spectrum of 4 '-bis (2, 4, 5-trimethyl-1H-imidazole) -1,1' -biphenyls of example 3 is consistent with the expected structure. 1 H NMR (400 MHz, DMSO) δ 7.93 (d, J = 8.2 Hz, 4H), 7.47 (d, J = 8.1 Hz, 4H), 2.12 (s, 6H), 2.09(s, 6H) 1.95 (s, 6H)。
As can be seen from fig. 5, the nuclear magnetic resonance spectrum of the ion-conducting cross-linked product prepared in step (3) of example 4 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the ratio of the signal intensity of the methylene group of chlorine corresponding to the shift of 4.66ppm to the signal intensity of the aromatic ring corresponding to the shift of 7.44-7.77ppm is decreased from 1:32.52 in FIG. 1 to 1 in FIG. 5: 40.03, indicating that step (3) of example 4 was subjected to the corresponding crosslinking reaction.
As can be seen from fig. 6, the nuclear magnetic hydrogen spectrum of the ion conducting polymer prepared in step (2) of example 5 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak with the displacement of 7.43-7.64ppm corresponds to the signal of H on the aromatic ring, the peak with the displacement of 4.55ppm corresponds to the signal of methylene on dibromoacetone, the peak with the displacement of 3.37ppm corresponds to the signal of methylene on N (overlapping with the water peak), the peak with the displacement of 3.15ppm corresponds to the signal of methyl on N, and the peak with the displacement of 2.84ppm corresponds to the signal of H on the piperidine ring of methylene not connected with N.
As can be seen from fig. 7, the nuclear magnetic hydrogen spectrum of the ion conducting polymer prepared in step (2) of example 6 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak with the displacement of 7.47-7.84ppm corresponds to the signal of H on the aromatic ring, the peak with the displacement of 4.60ppm corresponds to the signal of methylene on dibromoacetone, the peak with the displacement of 3.35ppm corresponds to the signal of methylene on N (overlapping with the water peak), the peak with the displacement of 3.16ppm corresponds to the signal of methyl on N, and the peak with the displacement of 2.90ppm corresponds to the signal of H on the piperidine ring of methylene not connected with N.
As can be seen from fig. 8, the nuclear magnetic hydrogen spectrum of the ion conducting polymer prepared in step (2) of example 7 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak with the displacement of 7.46-7.82ppm corresponds to the signal of H on the aromatic ring of the terphenyl, the peak with the displacement of 7.16-7.21ppm corresponds to the aromatic ring signal of the trifluoroacetophenone, the peak with the displacement of 4.60ppm corresponds to the methylene signal on dibromoacetone, the peak with the displacement of 3.39ppm corresponds to the signal of methylene on N (overlapped with the water peak), the peak with the displacement of 3.15ppm corresponds to the signal of methyl on N, and the peak with the displacement of 2.84-3.00ppm corresponds to the signal of H on the methylene which is not connected with N on the piperidine ring.
As can be seen from fig. 9, the nuclear magnetic hydrogen spectrum of the ion conducting polymer produced in step (2) of comparative example 1 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak with the displacement of 7.58-7.76ppm corresponds to the signal of H on the terphenyl aromatic ring, the peak with the displacement of 3.43ppm corresponds to the signal of methylene on N (overlapped with the water peak), the peak with the displacement of 3.16ppm corresponds to the signal of methyl on N, and the peak with the displacement of 2.87ppm corresponds to the signal of H on the piperidine ring which is not connected with N (the peak of 2.87 is an impurity interference signal and is not the signal in the product).
Experimental example 2
The swelling properties and ion conductivity of the anion exchange membranes prepared in examples 1 to 9 and comparative examples 1 to 2 were measured, respectively, and the measurement results are shown in table 1.
The swelling performance test method is as follows: and cutting the prepared anion exchange membrane into a square-sized (3 cm multiplied by 3 cm) membrane sample, soaking the membrane sample in deionized water for 12 hours at 25 ℃, taking out the membrane sample, rapidly wiping off residual liquid on the surface of the membrane sample by using filter paper, measuring four side lengths of the membrane sample, taking an average value of the four side lengths, and marking the average value as L1. Then, the film sample was baked at 60℃for 0.5 hours, four side lengths of the film sample in a dry film state were measured, and an average value of the four side lengths was taken and recorded as L2. The swelling ratio of the anion exchange membrane is calculated as follows: swelling ratio = [ (L2-L1)/L1 ] ×100%.
The ion conductivity test method is as follows: hydroxyl ion conductivity was tested by a vantolab PGSTAT128N electrochemical workstation in switzerland. The prepared anion exchange membrane is soaked in 1M KOH aqueous solution for 12 hours, and then is repeatedly washed by deionized water until the KOH solution on the surface is completely washed, and then hydroxide ion conductivity test is carried out by a four-probe method.
The test method of the alkali stability performance is as follows: the prepared anion exchange membrane is soaked in a 2M potassium hydroxide solution at 80 ℃ to test the time taken for the hydroxyl ion conductivity to be reduced by 10%.
TABLE 1
As can be seen from Table 1, the swelling ratios of the anion-exchange membranes prepared in examples 1 to 9 are lower than those of the anion-exchange membranes prepared in comparative examples 1 to 2, the ion conductivity of the anion-exchange membranes prepared in examples 1 to 9 is higher than that of the anion-exchange membranes prepared in comparative examples 1 to 2, and the alkali stability of the anion-exchange membranes prepared in examples 1 to 9 is higher than that of the anion-exchange membranes prepared in comparative examples 1 to 2, which indicates that the anion-exchange membranes prepared in examples 1 to 9 have better electrochemical properties and longer service lives.
Claims (10)
1. An ion-conducting cross-link characterized by the following structural formula:
；
Wherein m is 1 And m 2 Are all greater than or equal to 0, n 1 And n 2 All > 0, p 1 And p 2 All > 0, p 3 And p 4 All are more than or equal to 0; x and y are each independently 0 or 1, s and q are each not less than 0, x and s are not simultaneously 0, and y and q are not simultaneously 0; j and u are each independently 0 or 1, k and a are each 0 or more, j and k are not simultaneously 0, u and a are not simultaneously 0;
Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 ar, ar 8 Each independently selected from substituted or unsubstituted aryl;
R 1 、R 6 、R 7 、R 12 、R g r is as follows r Each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
R 2 r is as follows 8 Are all groups containing fluorine atoms;
R 30 r is as follows 31 All are halogen atoms;
R a r is as follows b Each independently is of the structure ofOr->；R 3 R is as follows 4 Each independently selected from the group consisting of substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, structures containing salt units, and hydrogen atoms; x is X 1 - X is as follows 2 - Are anions; w is a natural number of 1 to 6;
R f r is as follows h Each independently selected from the group consisting of a structure containing a salt unit, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a group containing a halogen atom;
R 5 r is as follows 11 Each independently selected from the group consisting of structures containing salt units, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, groups containing halogen atomsStructure of (C) containing- >Is of a structure of (2);
M 1 、M 2 m is as follows 3 Are all cross-linked structures; the cross-linked structure contains an amine group, or the cross-linked structure contains a positively charged ammonium group and an anion electrostatically bound to the positively charged ammonium group;
P 1 is a first ion-conducting polymer, P 2 Is a second ion conducting polymer.
2. The ion-conducting cross-link of claim 1, wherein the cross-linked structure has the structural formulaThe method comprises the steps of carrying out a first treatment on the surface of the Wherein v (X) a - ) Is an anion, v is a natural number of 1 to 4, z is a natural number of 1 to 4, and v=z; />The structural formula is as follows:
；
wherein R is 13 Selected from monocyclic aromatic groups, condensed ring aromatic groups or alkyl groups;
R 14 r is as follows 15 Are positively charged ammonium groups;
R 16 r is as follows 17 Each independently selected from the group consisting of a hydrogen atom, an amine group,、/>Substituted or unsubstituted alkyl, substituted or unsubstituted aryl; wherein T is 1 T is as follows 2 Are positively charged ammonium groups, P 3 Is a third ion-conducting polymer, P 4 Is a fourth ion conducting polymer.
3. The ion-conducting cross-link of claim 2, wherein the positively charged ammonium groups are selected from at least one of quaternary ammonium groups and positively charged cyclic amine groups;
or, the positively charged ammonium group is selected from at least one of quaternary ammonium group, imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium;
Or, the positively charged ammonium group is selected from at least one of quaternary ammonium group, imidazolium and piperidinium;
or, the positively charged ammonium group is selected fromAnd at least one of piperidinium;
or, R 13 Selected from phenyl, biphenyl, terphenyl, naphthyl and alkyl with the carbon number more than or equal to 2;
or, X a - At least one selected from the group consisting of a halogen ion, a p-toluenesulfonic acid anion and a trifluoromethanesulfonic acid anion.
4. The ion-conducting cross-link of claim 1, wherein the cross-linked structure has the following structural formula:
or->；
Wherein d is more than or equal to 1, and both c and t are more than or equal to 0;
R 18 、R 19 、R 20 、R 21 、R 22 and R is 23 Each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group;
R 24 r is as follows 25 Each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
R 26 r is as follows 27 Each independently selected from the group consisting of a hydrogen atom, a group containing a carbon-carbon double bond,、/>Substituted or unsubstituted alkyl, substituted or unsubstituted aryl; wherein T is 3 T is as follows 4 Are each substituted or unsubstituted alkyl, P 5 P being a fifth ion-conducting polymer 6 Is a sixth ion conducting polymer.
5. The ion-conducting cross-link of claim 1, wherein the cross-linked structure has the following structural formula:
、/>、/>、Or->The method comprises the steps of carrying out a first treatment on the surface of the Wherein d is greater than or equal to 1, R 13 Selected from phenyl, biphenyl, terphenyl, naphthyl and alkyl with more than or equal to 2 carbon atoms, X a - Is anionic.
6. The ion-conducting cross-linked of any of claims 1-5, wherein x and y are both 0;
or/and, s and q are each independently a natural number of 1 to 3;
or/and, j and u are both 0;
or/and, k and a are each independently a natural number of 1 to 3;
or/and, ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 Ar, ar 8 Each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted o-terphenyl, substituted or unsubstituted p-tetrabiphenyl, substituted or unsubstituted pentabiphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diethylfluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl ether, substituted or unsubstituted diphenyl sulfide, substituted or unsubstituted diphenyl sulfone, and substituted or unsubstituted diphenyl sulfoxide;
Or/and, R 1 R is as follows 7 All are phenyl groups;
or/and, R 2 R is as follows 8 Each independently selected from fluorine atom substituted alkyl or fluorine atom substituted aryl;
or/and, R f R is as follows h Each independently selected from C 1 ~C 3 C substituted by alkyl or halogen atoms 1 ~C 3 Alkyl of (a);
or/and, R 5 R is as follows 11 Each independently selected from C 1 ~C 3 C substituted by alkyl groups or halogen atoms 1 ~C 3 Is an alkyl group containingStructure or contain->Is of a structure of (2);
or/and, R a R is as follows b Is of the structure of；R 3 R is as follows 4 Each independently selected from the group consisting of substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, structures containing salt units, and hydrogen atoms; x is X 1 - Is an anion;
or/and, R 3 R is as follows 4 All being substituted or unsubstituted C 1 ~C 3 Alkyl of (a);
or/and, X 1 - X is as follows 2 - Each independently selected from at least one of a halogen ion, a p-toluenesulfonic acid anion, and a trifluoromethanesulfonic acid anion;
or/and, 25 percent or more of m 1 /(m 1 +n 1 +p 1 +p 3 )≥0，99.99%≥n 1 /(m 1 +n 1 +p 1 +p 3 )≥60%，25%≥(p 1 +p 3 )/(m 1 +n 1 +p 1 +p 3 )≥0.01%，25%≥m 2 /(m 2 +n 2 +p 2 +p 4 )≥0，99.99%≥n 2 /(m 2 +n 2 +p 2 +p 4 )≥60%，25%≥(p 2 +p 4 )/(m 2 +n 2 +p 2 +p 4 )≥0.01%；
Or/and the number average molecular weight of the ion-conducting cross-linked substance is 10000 Da-1000000 Da.
7. A method of making an ion-conducting cross-link, the ion-conducting cross-link comprising: carrying out a crosslinking reaction on a system containing an ion conducting polymer and a crosslinking agent; the cross-linking agent is a cross-linking agent containing amino groups; the structural formula of the ion conducting polymer is as follows:
；
Or, the preparation method of the ion-conducting crosslinked material comprises the following steps: carrying out a crosslinking reaction on a system containing a first polymer and a crosslinking agent; then adding a salifying substance into the system after the crosslinking reaction to carry out salifying reaction; the cross-linking agent is a cross-linking agent containing amino groups; the first polymer has the following structural formula:
；
wherein m is greater than or equal to 0, n is greater than 0, p is greater than 0, and x 1 0 or 1, s 1 Not less than 0 and x 1 And s 1 Not simultaneously 0;
Ar 1a 、Ar 2a ar, ar 3a Each independently selected from substituted or unsubstituted aryl;
R 1a r is as follows 6a Each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
R 2a is a group containing a fluorine atom;
R 5a a group selected from the group consisting of a structure containing a salt unit, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a halogen atom;
R 30 is a halogen atom;
R a1 the structural formula is as follows:or->；
R c The structural formula is as follows:or->；
The salifying substance comprises a first substance or/and a second substance, wherein the structural formula of the first substance is R d -R 39 The structural formula of the second substance is；
R 3a R is as follows 4a Each independently selected from the group consisting of substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, structures containing salt units, and hydrogen atoms; x is X 1a - X is as follows 2a - Are anions; w (w) 1 A natural number of 1 to 6; r is R d Selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted aryl, R 39 、R 9 R is as follows 10 Each independently selected from a halogen atom, a carbonate group or a sulfate group.
8. The method of preparing an ion-conducting cross-link according to claim 7, wherein the cross-linking agent has the following structural formula:
；
wherein R is 31 Selected from monocyclic aromatic groups, condensed ring aromatic groups or alkyl groups;
R 32 r is as follows 33 All have structures containing amino groups;
R 34 r is as follows 35 Each independently selected from the group consisting of a hydrogen atom, a structure containing an amine group, a substituted or unsubstituted alkyl group, a substituted or unsubstitutedUnsubstituted aryl;
or, the structural formula of the cross-linking agent is as follows:
；
wherein R is 36 Is a group containing a carbon-carbon double bond; r is R 37 R is as follows 38 Each independently selected from the group consisting of a hydrogen atom, a group containing a carbon-carbon double bond, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group.
9. An anion exchange membrane, wherein the anion exchange membrane comprises an ion-conducting cross-linked material;
or, the anion exchange membrane comprises a porous support layer and a filler filled in the pores of the porous support layer, wherein the filler comprises inorganic hydrophilic particles and ion conduction cross-links;
Or, the anion exchange membrane comprises a porous support layer and a filler filled in the pores of the porous support layer, wherein the filler comprises an ion-conducting cross-link;
or, the anion exchange membrane comprises inorganic hydrophilic particles and ion-conducting crosslinks;
wherein the ion-conducting crosslinked material is the ion-conducting crosslinked material according to any one of claims 1 to 6 or the ion-conducting crosslinked material produced by the method for producing an ion-conducting crosslinked material according to claim 7 or 8.
10. Use of an anion exchange membrane according to claim 9 for the preparation of an electrolyzed water device, an electrodialysis device, a fuel cell or an electrochemical energy storage device;
the electrochemical energy storage device comprises a flow battery.
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