CN117964855A - Single-ion conductive fluorine-containing copolymer and preparation method and application thereof - Google Patents
Single-ion conductive fluorine-containing copolymer and preparation method and application thereof Download PDFInfo
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- CN117964855A CN117964855A CN202410072041.5A CN202410072041A CN117964855A CN 117964855 A CN117964855 A CN 117964855A CN 202410072041 A CN202410072041 A CN 202410072041A CN 117964855 A CN117964855 A CN 117964855A
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- Prior art keywords
- ion
- fluorine
- ether
- reaction
- monomer
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 57
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000011737 fluorine Substances 0.000 title claims abstract description 49
- 229920001577 copolymer Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 trifluoro vinyl Chemical group 0.000 claims abstract description 52
- 150000002500 ions Chemical class 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000005286 illumination Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000002608 ionic liquid Substances 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000002000 Electrolyte additive Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical group FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001414 potassium ion Chemical group 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003983 crown ethers Chemical group 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- KSOCRXJMFBYSFA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,6,6,6-tridecafluoro-5-(1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluorohexan-2-yloxy)hexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KSOCRXJMFBYSFA-UHFFFAOYSA-N 0.000 claims description 2
- PGISRKZDCUNMRX-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-(trifluoromethoxy)butane Chemical compound FC(F)(F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F PGISRKZDCUNMRX-UHFFFAOYSA-N 0.000 claims description 2
- CXJWJJZGJZNBRK-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-(1,1,1,3,3,3-hexafluoropropan-2-yloxy)propane Chemical compound FC(F)(F)C(C(F)(F)F)OC(C(F)(F)F)C(F)(F)F CXJWJJZGJZNBRK-UHFFFAOYSA-N 0.000 claims description 2
- VNXYDFNVQBICRO-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-methoxypropane Chemical compound COC(C(F)(F)F)C(F)(F)F VNXYDFNVQBICRO-UHFFFAOYSA-N 0.000 claims description 2
- ZIZMDHZLHJBNSQ-UHFFFAOYSA-N 1,2-dihydrophenazine Chemical compound C1=CC=C2N=C(C=CCC3)C3=NC2=C1 ZIZMDHZLHJBNSQ-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000008062 acetophenones Chemical class 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- VFGGFRZVTZVOBE-UHFFFAOYSA-K aluminum titanium(4+) phosphate Chemical compound [Ti+4].P(=O)([O-])([O-])[O-].[Al+3] VFGGFRZVTZVOBE-UHFFFAOYSA-K 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 claims description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical class C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- WZWSOGGTVQXXSN-UHFFFAOYSA-N cyclohexanone;toluene Chemical compound CC1=CC=CC=C1.O=C1CCCCC1 WZWSOGGTVQXXSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012990 dithiocarbamate Substances 0.000 claims description 2
- 150000004659 dithiocarbamates Chemical class 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 2
- 150000002432 hydroperoxides Chemical class 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical class FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 125000006337 tetrafluoro ethyl group Chemical group 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 2
- 239000012989 trithiocarbonate Substances 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012991 xanthate Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims 1
- 239000002227 LISICON Substances 0.000 claims 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000002223 garnet Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000005496 phosphonium group Chemical group 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 229920001940 conductive polymer Polymers 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 7
- 230000005012 migration Effects 0.000 abstract description 7
- 238000013508 migration Methods 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 3
- 238000012704 multi-component copolymerization Methods 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- 239000005518 polymer electrolyte Substances 0.000 description 12
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- GWTYBAOENKSFAY-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-2-(1,2,2-trifluoroethenoxy)ethane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)F GWTYBAOENKSFAY-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NOPJRYAFUXTDLX-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane Chemical compound COC(F)(F)C(F)(F)C(F)(F)F NOPJRYAFUXTDLX-UHFFFAOYSA-N 0.000 description 1
- VQUGQIYAVYQSAB-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-2-(1,2,2-trifluoroethenoxy)ethanesulfonyl fluoride Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)S(F)(=O)=O VQUGQIYAVYQSAB-UHFFFAOYSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000000666 effect on cation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
Landscapes
- Secondary Cells (AREA)
Abstract
The invention provides a single-ion conductive fluorine-containing copolymer and a preparation method and application thereof, belonging to the technical field of ion batteries. The monomer is polymerized in multiple modes by taking fluorine-containing ionic monomer, trifluoro vinyl monomer and vinyl monomer as comonomers and heating or illumination. The multi-functional segments are introduced into the polymer molecular chain through multi-component copolymerization, so that more selectivity is provided for the structural design of the single ion conductive polymer, and the combined action of different functional segments improves the comprehensive electrochemical performance of the electrolyte. The single-ion conductive fluorine-containing copolymer obtained by the method has good room temperature conductivity, lithium ion migration number, high pressure resistance, mechanical property and interface compatibility.
Description
Technical Field
The invention belongs to the technical field of ion batteries, and particularly relates to a preparation method of a single-ion conductive fluorine-containing copolymer and application of an electrolyte thereof.
Background
The polymer electrolyte has good flexibility, high electrochemical stability and proper mechanical strength, and has good application prospect in wearable flexible electronic equipment. However, in the polymer electrolyte represented by polyethylene oxide (PEO), since the polymer has a crystalline region which is unfavorable for ion conduction, and cations and anions can move freely in an amorphous region, the oxygen atoms on the main chain have a strong coordination and binding effect on cations, so that the cation migration number of the polymer electrolyte is relatively low. These factors all lead to lower ionic conductivity of the polymer electrolyte at room temperature, serious polarization of the battery, and easy penetration of dendrites to cause short circuit failure of the battery, thus limiting practical application of the polymer electrolyte in the battery.
Unlike traditional polymer electrolyte, the single ion conductive polymer fixes the anionic group on the polymer chain through chemical bond, only the cation in the system can move, the current in the battery is all contributed by the movement of the cation, the migration number of the cation is close to 1, which is far higher than that of the traditional PEO polymer electrolyte, and the concentration polarization degree of the system is reduced. However, the single ion conductive polymer electrolyte has low ionic conductivity at room temperature due to the movement of cations only, and the practical application of the battery is still difficult to realize.
Therefore, how to design a single ion conductive polymer electrolyte with good comprehensive electrochemical performance through the design of a single structure becomes a technical problem to be solved.
Disclosure of Invention
In view of the above, a first technical object of the present invention is to provide a single ion conductive fluorocopolymer which solves the problems in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A single ion conductive fluorine-containing copolymer having a unit structural formula represented by the formula (1):
Wherein R 1,R2,R3 is fluorine atom or C1-3 perfluoroalkane chain, R 4 is C1-10 perfluoroether chain or C0-3 alkane chain, R 5 is carbonyl or sulfonyl, R 6 is sulfonyl or acyl, R 7 is chlorine atom, trifluoromethyl or C1-10 perfluoroether chain; r 8 is an ester group or an alkoxy group; m is sodium ion, lithium ion, zinc ion, magnesium ion, aluminum ion or potassium ion; m is a positive integer, and m is more than or equal to 10 and less than or equal to 100; n is a positive integer, and n is more than or equal to 10 and less than or equal to 100; k is a positive integer, and k is more than or equal to 10 and less than or equal to 100.
It should be noted that, because of the small radius of fluorine atom and strong electronegativity, the fluorine atom is introduced into the polymer through the C-F bond, so that the fluorine-containing polymer has a plurality of unique physicochemical properties, such as chemical corrosion resistance, high stability, oxidation resistance, difficult combustion and other excellent properties. By introducing other functional segments into the molecular structure of the fluorine-containing polymer in a copolymerization mode, the crystallinity of the fluorine-containing polymer can be effectively reduced, and the phase separation between fluorine-philic and non-fluorine-philic parts can be furthest reduced. Therefore, the invention designs the monomer structure, introduces characteristic functional groups into the polymer through multi-monomer copolymerization, provides more selectivity for the structural design of the single ion conductive polymer, and finally realizes the improvement of the comprehensive electrochemical performance of the single ion conductive fluorine-containing copolymer electrolyte.
The second technical purpose of the invention is to provide a preparation method of the single-ion conductive fluorine-containing copolymer.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The preparation process of the single ion conducting fluorine-containing copolymer is based on the multipolymer reaction of fluorine-containing ion monomer, trifluoro vinyl monomer and vinyl monomer.
Preferably, the structural formula of the fluorine-containing ionic monomer is shown as formula (2) or formula (3):
Wherein R 1,R2,R3 is fluorine atom or perfluoro alkane chain with 1-3 carbon units, R 4 is alkane chain with 0-3 carbon units, R 5 is carbonyl or sulfonyl, R 6 is fluorine atom, chlorine atom, cyano group, trifluoromethyl substituted alkane chain with 1-6 carbon units, phenyl group, p-trifluoromethylphenyl or p-methoxyphenyl, R 7 is perfluoro ether chain with 1-10 carbon units, M is sodium ion, lithium ion, zinc ion, magnesium ion, aluminum ion or potassium ion.
Preferably, the structural formula of the trifluoro vinyl monomer is shown as a formula (4), and the structural formula of the vinyl monomer is shown as a formula (5) or a formula (6):
Wherein R 1 is chlorine atom, trifluoromethyl or perfluoro ether chain with 1-10 carbon units, R 2 is methyl, ethyl or tertiary butyl with 12-24 carbon units, R 3 is methyl, tertiary butyl, ethoxyformyl, dimethyl tertiary butylsiloxy or crown ether group with 12-24 carbon units.
Specifically, the preparation method of the single ion conductive fluorine-containing copolymer comprises the following steps:
(1) Preparing a gas solution: and (3) injecting a solvent into the reaction kettle under the nitrogen atmosphere, and slowly filling the reaction kettle with the gaseous monomer at the temperature of minus 40 ℃.
(2) Preparing a reaction solution: the reactants comprise a fluorine-containing ionic monomer, a trifluoro vinyl monomer, a solvent, a reaction additive and an electrolyte additive, and the fluorine-containing ionic monomer is calculated by mole ratio: trifluoroethyl group monomer: vinyl monomer=10 (3 to 30): 10 to 50; fluorine-containing ionic monomer: reactive additive = 1000, (1-300); the reactants are mixed uniformly, oxygen in the reaction system is removed, and the reaction is carried out under the stirring condition.
(3) And after the reaction is finished, taking out the solution after the reaction, purifying and separating out the polymer, and drying the polymer in a vacuum drying oven at 60-100 ℃ for 24-48 hours to obtain the polymer.
And, for the reaction of monomers containing gaseous species, the preparation step thereof is carried out starting from step (1); for reactions that do not contain monomers of the gas type, the preparation step starts from step (2).
Further preferred, the reaction additive is one or more of azo compounds, acyl peroxides, hydroperoxides, dialkyl peroxides, ester peroxides, ketone peroxides, dicarbonate peroxides, dithiocarbonates, trithiocarbonates, xanthates, dithiocarbamates, perfluoroalkyl halides, alkyl halides, benzophenone compounds, aromatic ketone compounds, acetophenone derivatives, benzil derivatives, alpha-hydroxy ketone compounds, acyl phosphine oxides, porphyrin compounds, dihydrophenazine, phenothiazine, phenoxazine; the solvent is one or a plurality of combinations of dimethyl sulfoxide, dimethyl ether, cyclohexane, methyl ethyl ketone, dimethyl sulfide, 1, 3-dioxolane, hexafluoroisopropyl ether, N-dimethylformamide, methyl butanone, butyl acetate, methyl isobutyl ketone, tetrafluoroethyl tetrafluoropropyl ether, cyclohexanone, pentane, butyl propionate, hexane, octane, toluene cyclohexanone, xylene, carbonates, hexafluoroisopropyl methyl ether, methyl acetate, isopropyl ether, propylene oxide, ethylene glycol dimethyl ether, N-methylpyrrolidone, tetrafluoroethyl octafluoropentyl ether, 1, 4-dioxane, butanone, ethyl acetate benzene, propyl propionate, perfluorobutyl methyl ether, acetonitrile, propyl acetate, bistrifluoroethyl ether, chlorobenzene, perfluorobutyl ethyl ether, 1, 2-dimethoxyethane, crown ether and tetrahydrofuran.
Further preferably, the reaction condition in the step (2) is heating, the heating temperature is 60-120 ℃, and the reaction is carried out for 1-24 hours under the stirring condition; when the reaction condition of the step (2) is illumination, a light source with the emission wavelength of 350-700 nm is used for reacting for 1-12 hours under the stirring condition.
A third object of the present invention is to provide the use of a single ion conductive fluorocopolymer as described above for the preparation of an ion battery.
In particular to the application of the single ion conductive fluorine-containing copolymer in an electrolyte of an ion battery; the electrolyte comprises a single ion conductive fluorine-containing copolymer and an electrolyte additive, wherein the mass fraction of the electrolyte additive in the single ion conductive fluorine-containing copolymer is 5-25%.
Further, the electrolyte additive is one or more of bis (trifluoromethanesulfonyl imide), bis (fluorosulfonyl imide), trifluoromethyl sulfonate, hexafluoroarsenate, tetrafluoroborate, iodized salt, nitrate, perchlorate, difluoroethanedioic borate, bisoxalato borate, hexafluorophosphate, titanium aluminum phosphate, sulfate, garnet-type material, LISICON-type material, NASICION-type material, perovskite-type material, sulfide, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, carbonate, carboxylic acid esters, dimethyl sulfoxide, imidazole-type ionic liquid, indazole-type ionic liquid, pyrimidine-type ionic liquid, pyrrolidine-type ionic liquid, pyridine-type ionic liquid, morpholine-type ionic liquid, piperidine-type ionic liquid, quaternary ammonium-type ionic liquid, phosphonium-type ionic liquid, guanidine-type ionic liquid; the ion battery is a sodium ion battery, a lithium ion battery, a zinc ion battery, a magnesium ion battery, an aluminum ion battery or a potassium ion battery.
For the sake of fully disclosing the technical scheme related to the present invention, a preparation method for preparing an ion battery is specifically disclosed, but the disclosure should not be construed as limiting the application of the single ion conductive fluorine-containing copolymer in preparing an ion battery, and all the preparation methods using the single ion conductive fluorine-containing copolymer belong to the protection scope of the present invention.
Optionally, the preparation method of the lithium ion battery comprises the following steps:
And assembling the polymer electrolyte between the positive electrode plate and the negative electrode plate, and performing heat treatment and packaging treatment to obtain the battery. The processes of battery pole piece preparation, heat treatment, encapsulation and the like related in the steps belong to conventional test means in the field.
Preferably, the active material in the positive electrode sheet is phosphide, chalcogenide, vanadium oxide, metal sulfide, manganese oxide or nickel-manganese-cobalt composite oxide. The active material of the negative electrode plate is a sodium negative electrode, a lithium negative electrode, a zinc negative electrode, a magnesium negative electrode, an aluminum negative electrode or a potassium negative electrode. The sodium negative electrode, the lithium negative electrode, the zinc negative electrode, the magnesium negative electrode, the aluminum negative electrode or the potassium negative electrode can be one or a combination of a plurality of sodium metal, lithium metal, zinc metal, magnesium metal, aluminum metal, potassium metal simple substance or alloy thereof, graphene, carbon material, nitride, boron-based material, silicon-based material and phosphide on the current collector.
Compared with the prior art, the invention has the following excellent effects:
The invention discloses a single ion conductive fluorine-containing copolymer, which takes fluorine-containing ion monomers, trifluoro vinyl monomers and vinyl monomers as comonomers, and realizes the multi-element copolymerization of the monomers in a heating or illumination mode, thereby providing more selectivity for the structural design of single ion conductive polymers. The multipolymer is copolymerized to introduce different functional segments into the polymer, and the combined action of the functional segments improves the comprehensive performance of the electrolyte and can also minimize the phase separation between the fluorine-philic part and the non-fluorine-philic part in the fluorine-containing polymer. The polymer electrolyte, the positive electrode plate and the negative electrode plate are directly assembled into a battery for experimental test, and the result shows that the single ion conductive fluorine-containing copolymer has good ion conductivity and cation migration number at room temperature, and has good high-voltage resistance, negative electrode interface compatibility and thermal stability.
Drawings
In order to more clearly illustrate the embodiments and technical solutions of the present invention, the following description will briefly explain the embodiments of the present invention or the drawings required to be used in the prior art solutions, and it is apparent that the drawings in the following description are only a part of the embodiments of the present invention, and other drawings may be obtained according to the drawings provided.
FIG. 1 is a synthetic route for synthesizing a single ion conductive fluorocopolymer monomer in example 1.
FIG. 2 is a synthetic route for the polyethylene glycol vinyl ether in example 2.
FIG. 3 is a 1 H nuclear magnetic spectrum of polyethylene glycol vinyl ether prepared in example 2.
FIG. 4 is a synthetic route for the polymer synthesized in example 3.
FIG. 5 is a thermal weight curve of the polymer synthesized in example 3.
FIG. 6 is a synthetic route for the polymer synthesized in example 4.
FIG. 7 is a graph showing the permeation chromatography flow-out time of the polymer gel synthesized in example 4.
Fig. 8 is a current-time curve of the lithium metal battery in application example 2.
Fig. 9 is a graph showing the relationship between the cycle time and the peeling/deposition of lithium at 30 c in the lithium metal battery of application example 3.
Fig. 10 is an electron scanning microscope image of a lithium sheet after 100 hours of lithium exfoliation/deposition cycle at 30 c using the lithium metal battery of example 3.
FIG. 11 is a schematic illustration of the application of the single ion conductive fluorocopolymer electrolyte of the invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The word "embodiment" as used herein does not necessarily mean that any embodiment described as "exemplary" is preferred or advantageous over other embodiments. Performance index testing in the examples of the present application, unless otherwise specified, was performed using conventional testing methods in the art. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; other test methods and techniques not specifically mentioned in the present application are those commonly used by those skilled in the art.
Numerous specific details are set forth in the following examples in order to provide a better understanding of the present application. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In the examples, some methods, means, instruments, devices, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present application.
On the premise of no conflict, the technical features disclosed by the embodiment of the application can be combined at will, and the obtained technical scheme belongs to the disclosure of the embodiment of the application.
The invention realizes the copolymerization of the multi-element monomers by heating or illumination. The multi-functional segments are introduced into the polymer molecular chain through multi-component copolymerization, and the combined action of different functional segments improves the comprehensive performance of the electrolyte, can also minimize the phase separation between fluorine-philic and non-fluorine-philic parts in the fluorine-containing polymer, and provides more selectivity for the structural design of the single ion conductive polymer. The single-ion conductive fluorine-containing copolymer obtained by the method has good room temperature conductivity, lithium ion migration number, high pressure resistance, mechanical property and interface compatibility.
For a better understanding of the present invention, the following examples are set forth to illustrate the present invention further in detail with respect to M as lithium ion, but are not to be construed as limiting the invention, and are intended to be within the scope of the present invention as defined by the appended claims.
A first part: synthesis of Single ion conductive fluorocopolymer monomer
Example 1
Trifluoroacetamide (14.8 g,100 mmol) and solvent water (100 mL) are added into a round bottom flask with a stirrer, lithium hydroxide aqueous solution is added until the pH value is in the range of 7-8, and the solvent water is removed; acetonitrile solvent (100 mL) was injected under nitrogen atmosphere and hexamethyldisilazane (32.2 g,200 mmol) was reacted with stirring at 110 ℃ overnight, after the reaction was completed acetonitrile and excess hexamethyldisilazane were removed; acetonitrile solvent (50 mL) and perfluoro (3-oxapent-4-ene) sulfonyl fluoride (18.9 g,50 mmol) were injected under nitrogen atmosphere, reacted at 80 ℃ for 12h, then the solvent was removed, and the crude product was subjected to column chromatography separation and purification to obtain yellow viscous solid perfluoro (3-oxapent-4-ene) trifluoromethanesulfonyl imide lithium. FIG. 1 is a synthetic route for synthesizing a single ion conductive fluorocopolymer monomer in example 1.
Example 2
2-Ethyleneoxyethanol (4.4 g,50 mmol), 4-dimethylaminopyridine (0.15 g,1.2 mmol), triethylamine (7.6 g,75 mmol) and tetrahydrofuran solvent (50 mL) were added to a round bottom flask equipped with a stirrer, and a solution of p-toluenesulfonyl chloride (11.5 g,60 mmol) in tetrahydrofuran (10 mL) was added dropwise at 0deg.C and the reaction stirred for 12h. After the reaction is finished, filtering and removing tetrahydrofuran, and separating and purifying the crude product by column chromatography to obtain colorless transparent liquid 2- (vinyloxy) -4-methylbenzenesulfonate.
Polyethylene glycol monomethyl ether (11.0 g,20mmol, average molecular weight 550 g/mol), sodium hydride (0.96 g,40 mmol) and tetrahydrofuran solvent (200 mL) were added to a round bottom flask with a stirrer, stirred for 3h, and then the mixture was injected with a tetrahydrofuran solution of 2- (ethyleneoxy) -4-methylbenzenesulfonate and stirred at room temperature overnight. And removing tetrahydrofuran after the reaction is finished, and separating and purifying the crude product by column chromatography to obtain colorless transparent liquid polyethylene glycol vinyl ether. FIG. 2 is a synthetic route for preparing synthetic polyethylene glycol vinyl ether of example 2. FIG. 3 is a 1 H nuclear magnetic spectrum of polyethylene glycol vinyl ether obtained in example 2.
A second part: synthesis of Poly (fluoride-containing ion-trifluoroethylene-vinyl) copolymer
Example 3
Heating to prepare poly (perfluoro (3-oxapent-4-ene) trifluoro methylsulfonylimine lithium-tetrafluoroethylene-polyethylene glycol vinyl ether) copolymer:
According to the perfluoro (3-oxapent-4-ene) triflimide lithium: tetrafluoroethylene: polyethylene glycol vinyl ether=10:3:40 molar ratio was dissolved in anhydrous diethyl carbonate, wherein the perfluoro (3-oxapent-4-ene) triflimide lithium was 10mmol. According to the fluorine-containing ionic monomer: reaction additive = 100:1 molar ratio, 0.1mmol of xylenoyl peroxide was added, dissolved and stirred uniformly, the reaction mixture was degassed and deoxygenated, and then the reaction vessel was reacted at 70 ℃ for 24h. After the reaction was completed, the product was precipitated three times with diethyl ether, and then the product was transferred to a vacuum oven at 70 ℃ and dried to constant weight to give a yellow viscous solid. FIG. 4 shows the synthetic route of the polymer synthesized in example 3, and FIG. 5 shows the thermogravimetric curve of the polymer synthesized in example 3, corresponding to a temperature of 278℃at a mass loss of 5%, the copolymer having good thermal stability.
Example 4
Preparation of poly (perfluoropropyl methyl ether-perfluoro (3-oxapent-4-ene) trifluoromethanesulfonyl imide lithium-chlorotrifluoroethylene-vinyl pivalate) copolymer by illumination:
Anhydrous diethyl carbonate is injected into a container under the nitrogen atmosphere, and the container is slowly filled with chlorotrifluoroethylene monomer at the temperature of minus 40 ℃ for reaction, and the perfluoropropyl methyl ether is prepared by the following steps: perfluoro (3-oxapent-4-ene) triflimide lithium: chlorotrifluoroethylene: vinyl pivalate = 15:10:10:30 molar ratio to the reaction vessel, wherein the lithium perfluoro (3-oxapent-4-ene) trifluoromethanesulfonyl imide is 10mmol; according to the fluorine-containing ionic monomer: reaction additive = 4:1 molar ratio 1mmol of ethyl 2- (ethoxythiocarbonyl) thiopropionate and 1.5mmol of phenoxazine are added, and the reaction mixture is evenly stirred for deaeration and deoxygenation; placing the reaction system in a 13W white LED lamp, reacting for 12 hours under irradiation with the wavelength ranging from 400nm to 700nm, precipitating the sample with diethyl ether three times, and then transferring the product into a vacuum drying oven at 70 ℃ for drying to constant weight, thus obtaining a yellowish viscous solid. The molecular weight of the polymer M n＝3.33×104 g/mol, as measured by GPC, was 1.24. FIG. 6 is a synthetic route for the polymer synthesized in example 4, and FIG. 7 is a graph showing the flow-out time of the polymer gel permeation chromatography synthesized in example 4.
Example 5
Uniformly mixing the polymer obtained in the example 3 with an electrolyte additive to obtain a single-ion conductive fluorine-containing copolymer electrolyte, wherein the mass fraction of the single-ion conductive fluorine-containing copolymer is 85%, and the mass fraction of the electrolyte additive is 15%; specifically, the electrolyte additive comprises the following components in percentage by mass:
5% of lithium iodide, 5% of N, N-dimethylformamide and 5% of lithium bistrifluoromethane sulfonyl imide.
Example 6
Uniformly mixing the polymer obtained in the example 4 with an electrolyte additive to obtain a single-ion conductive fluorine-containing copolymer electrolyte, wherein the mass fraction of the single-ion conductive fluorine-containing copolymer is 75%, and the mass fraction of the electrolyte additive is 25%, and specifically the electrolyte additive comprises the following components in percentage by mass:
5% of lithium nitrate, 5% of lithium aluminum titanium phosphate, 5% of 1-ethyl-3-methylimidazole bis (fluorosulfonyl) imide lithium and 10% of diethyl carbonate. Third section: electrolyte was assembled into a battery and electrochemical properties were measured
Application example 1
The electrolyte is assembled between two metal lithium pole pieces, the battery is obtained after heat treatment and encapsulation, and the conductivity of the battery is tested through an electrochemical workstation CHI660E at room temperature. The polymer electrolytes obtained in examples 5 and 6 were assembled between a stainless steel gasket and a lithium sheet, heat-treated, and packaged to obtain a battery, and the oxidation resistance voltage of the battery was measured at room temperature by an electrochemical workstation CHI660E, and the results of the ion conductivity and the oxidation resistance voltage at room temperature are summarized in table 1.
TABLE 1
The single-ion conductive fluorine-containing copolymer has higher oxidation resistance voltage, can be assembled into a battery with a high-voltage positive electrode material such as nickel cobalt lithium manganate (NCM), and has high discharge capacity.
Application example 2:
The single ion conductive fluorine-containing copolymer electrolyte obtained in example 5 is assembled between two metal lithium pole pieces, and after heat treatment and encapsulation, a symmetrical lithium metal battery is obtained, and the lithium migration number is 0.91 at room temperature through an electrochemical workstation CHI660E test. Fig. 8 is a current-time curve of the lithium metal battery in application example 2.
The single ion conductive fluorine-containing copolymer electrolyte has a migration number close to 1, so that concentration polarization phenomenon in a battery is relieved, and further growth of lithium dendrites is effectively inhibited.
Application example 3:
The single ion conductive fluorine-containing copolymer electrolyte obtained in example 6 is assembled between two metal lithium pole pieces, and after heat treatment and encapsulation, a symmetrical lithium metal battery is obtained, and lithium stripping/deposition cycle test of the battery is carried out at 30 ℃ through a blue electric test system at a current density of 0.5mA/cm 2. Fig. 9 is a graph showing the relationship between the cycle time and the peeling/deposition of lithium at 30 c in the lithium metal battery of application example 3. Fig. 10 is an electron scanning microscope image of a lithium sheet after 100 hours of lithium peeling/deposition cycle at 30 c with a current density of 0.5mA/cm 2 for the lithium metal battery of application example 3.
The single ion conductive fluorine-containing copolymer electrolyte shows stable lithium stripping/deposition cycle behavior, and is more intuitively shown by an electron scanning microscope image, so that the single ion conductive fluorine-containing copolymer electrolyte and a lithium metal electrode have good compatibility, and short circuit does not appear in the stable cycle for 700 hours under the current density of 0.5mA/cm 2.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A single ion conductive fluorine-containing copolymer is characterized by having a unit structural formula shown in formula (1):
Wherein R 1,R2,R3 is fluorine atom or C1-3 perfluoroalkane chain, R 4 is C1-10 perfluoroether chain or C0-3 alkane chain, R 5 is carbonyl or sulfonyl, R 6 is sulfonyl or acyl, R 7 is chlorine atom, trifluoromethyl or C1-10 perfluoroether chain; r 8 is an ester group or an alkoxy group; m is sodium ion, lithium ion, zinc ion, magnesium ion, aluminum ion or potassium ion; m is a positive integer, and m is more than or equal to 10 and less than or equal to 100; n is a positive integer, and n is more than or equal to 10 and less than or equal to 100; k is a positive integer, and k is more than or equal to 10 and less than or equal to 100.
2. A method for preparing the single-ion conductive fluorine-containing copolymer according to claim 1, wherein the preparation method is based on a multi-copolymerization reaction of a fluorine-containing ionic monomer, a trifluorovinyl monomer and a vinyl monomer.
3. The preparation method according to claim 2, wherein the structural formula of the fluorine-containing ionic monomer is represented by formula (2) or formula (3):
Wherein R 1,R2,R3 is fluorine atom or perfluoro alkane chain with 1-3 carbon units, R 4 is alkane chain with 0-3 carbon units, R 5 is carbonyl or sulfonyl, R 6 is fluorine atom, chlorine atom, cyano group, trifluoromethyl substituted alkane chain with 1-6 carbon units, phenyl group, p-trifluoromethylphenyl or p-methoxyphenyl, R 7 is perfluoro ether chain with 1-10 carbon units, M is sodium ion, lithium ion, zinc ion, magnesium ion, aluminum ion or potassium ion.
4. The production method according to claim 2, wherein the structural formula of the trifluorovinyl monomer is represented by formula (4), and the structural formula of the vinyl monomer is represented by formula (5) or formula (6):
Wherein R 1 is chlorine atom, trifluoromethyl or perfluoro ether chain with 1-10 carbon units, R 2 is methyl, ethyl or tertiary butyl with 12-24 carbon units, R 3 is methyl, tertiary butyl, ethoxyformyl, dimethyl tertiary butylsiloxy or crown ether group with 12-24 carbon units.
5. The preparation method according to any one of claims 2 to 4, characterized in that it comprises in particular the following steps:
(1) Preparing a gas solution: injecting a solvent into the reaction kettle under the nitrogen atmosphere, and slowly filling a gaseous monomer into the reaction kettle at the temperature of minus 40 ℃;
(2) Preparing a reaction solution: the reactants comprise fluorine-containing ionic monomer, trifluoro vinyl monomer, solvent and reaction additive, and the molar ratio is calculated by the fluorine-containing ionic monomer: trifluoroethyl group monomer: vinyl monomer=10 (3 to 30): 10 to 50; fluorine-containing ionic monomer: reactive additive = 1000, (1-300); uniformly mixing reactants, removing oxygen in a reaction system, and reacting under the stirring condition;
(3) After the reaction is finished, taking out the solution after the reaction, purifying and separating out the polymer, and drying the polymer in a vacuum drying oven at 60-100 ℃ for 24-48 hours to obtain the polymer;
And, for the reaction of monomers containing gaseous types, the preparation step is carried out starting from step (1); for reactions that do not contain monomers of the gas type, the preparation step starts from step (2).
6. The method according to claim 5, wherein the reaction additive is one or more of azo compounds, acyl peroxides, hydroperoxides, dialkyl peroxides, ester peroxides, ketone peroxides, dicarbonate peroxides, dithiocarbonates, trithiocarbonates, xanthates, dithiocarbamates, perfluoroalkyl halides, alkyl halides, benzophenone compounds, aromatic ketone compounds, acetophenone derivatives, benzil derivatives, α -hydroxyketone compounds, acylphosphine oxides, porphyrin compounds, dihydrophenazine, phenothiazine, phenoxazine; the solvent is one or a plurality of combinations of dimethyl sulfoxide, dimethyl ether, cyclohexane, methyl ethyl ketone, dimethyl sulfide, 1, 3-dioxolane, hexafluoroisopropyl ether, N-dimethylformamide, methyl butanone, butyl acetate, methyl isobutyl ketone, tetrafluoroethyl tetrafluoropropyl ether, cyclohexanone, pentane, butyl propionate, hexane, octane, toluene cyclohexanone, xylene, carbonates, hexafluoroisopropyl methyl ether, methyl acetate, isopropyl ether, propylene oxide, ethylene glycol dimethyl ether, N-methylpyrrolidone, tetrafluoroethyl octafluoropentyl ether, 1, 4-dioxane, butanone, ethyl acetate benzene, propyl propionate, perfluorobutyl methyl ether, acetonitrile, propyl acetate, bistrifluoroethyl ether, chlorobenzene, perfluorobutyl ethyl ether, 1, 2-dimethoxyethane, crown ether and tetrahydrofuran.
7. The preparation method according to claim 5, wherein the reaction condition in the step (2) is heating, the heating temperature is 60-120 ℃, and the reaction is carried out for 1-24 hours under stirring; when the reaction condition of the step (2) is illumination, a light source with the emission wavelength of 350-700 nm is used for reacting for 1-12 hours under the stirring condition.
8. Use of the single ion conductive fluorocopolymer as claimed in claim 1 in an ion battery.
9. The use according to claim 8, characterized in that the single ion conducting fluorocopolymer is used as electrolyte in an ion battery.
10. The use according to claim 9, wherein the electrolyte comprises a single ion conductive fluorocopolymer and an electrolyte additive, and the mass fraction of the electrolyte additive in the single ion conductive fluorocopolymer is 5-25%.
The electrolyte additive is one or a plurality of combinations of bis (trifluoromethanesulfonyl) imide salt, bis (fluorosulfonyl) imide salt, trifluoromethyl sulfonate, hexafluoroarsenate, tetrafluoroborate, iodized salt, nitrate, perchlorate, difluoroethanedioic borate, bisoxalato borate, hexafluorophosphate, titanium aluminum phosphate, sulfate, garnet type material, LISICON type material, NASICION type material, perovskite type material, sulfide, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, carbonic ester, carboxylic ester, dimethyl sulfoxide, imidazole type ionic liquid, indazole type ionic liquid, pyrimidine type ionic liquid, pyrrolidine type ionic liquid, pyridine type ionic liquid, morpholine type ionic liquid, piperidine type ionic liquid, quaternary ammonium type ionic liquid, quaternary phosphonium type ionic liquid and guanidine type ionic liquid; the ion battery is a sodium ion battery, a lithium ion battery, a zinc ion battery, a magnesium ion battery, an aluminum ion battery or a potassium ion battery.
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