CN105655640B - A kind of nonaqueous electrolytic solution and the lithium ion battery containing the electrolyte - Google Patents
A kind of nonaqueous electrolytic solution and the lithium ion battery containing the electrolyte Download PDFInfo
- Publication number
- CN105655640B CN105655640B CN201610183641.4A CN201610183641A CN105655640B CN 105655640 B CN105655640 B CN 105655640B CN 201610183641 A CN201610183641 A CN 201610183641A CN 105655640 B CN105655640 B CN 105655640B
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- CN
- China
- Prior art keywords
- electrolytic solution
- nonaqueous electrolytic
- unsubstituted
- alkyl
- silicon substrate
- Prior art date
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- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 239000003792 electrolyte Substances 0.000 title claims description 27
- -1 sulfate compound Chemical class 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010703 silicon Substances 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 238000006467 substitution reaction Methods 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000002955 isolation Methods 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 229960002645 boric acid Drugs 0.000 claims description 3
- 235000010338 boric acid Nutrition 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- YYSONLHJONEUMT-UHFFFAOYSA-N pentan-3-yl hydrogen carbonate Chemical compound CCC(CC)OC(O)=O YYSONLHJONEUMT-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- ATVLVRVBCRICNU-UHFFFAOYSA-N trifluorosilicon Chemical compound F[Si](F)F ATVLVRVBCRICNU-UHFFFAOYSA-N 0.000 claims description 3
- BZLZKLMROPIZSR-UHFFFAOYSA-N triphenylsilicon Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)C1=CC=CC=C1 BZLZKLMROPIZSR-UHFFFAOYSA-N 0.000 claims description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 10
- 125000004122 cyclic group Chemical group 0.000 abstract description 6
- 238000002161 passivation Methods 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 238000012360 testing method Methods 0.000 description 19
- 230000006872 improvement Effects 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PLAWCFOMHQCJBK-UHFFFAOYSA-N 1-(2,2-dimethylpropylperoxy)pentane Chemical group CCCCCOOCC(C)(C)C PLAWCFOMHQCJBK-UHFFFAOYSA-N 0.000 description 1
- 125000004825 2,2-dimethylpropylene group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- AOANMOLKQQXRCC-UHFFFAOYSA-N C(C)(=O)OC=C.C(O)(=O)F Chemical compound C(C)(=O)OC=C.C(O)(=O)F AOANMOLKQQXRCC-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013098 LiBF2 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WYWLPUYJUPVXSK-UHFFFAOYSA-N boron;oxalic acid Chemical compound [B].OC(=O)C(O)=O WYWLPUYJUPVXSK-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001887 cyclopentyloxy group Chemical group C1(CCCC1)O* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 150000003577 thiophenes Chemical class 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
The application belongs to field of lithium ion battery, specifically, is related to a kind of nonaqueous electrolytic solution and the lithium ion battery using the nonaqueous electrolytic solution.The nonaqueous electrolytic solution of the application includes non-aqueous organic solvent, lithium salts and additive, contains silicon substrate sulfate compound and 3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] alkyl compounds in additive.The application passes through 3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] alkyl compounds and silicon substrate sulfate compound synergistic effect, stable composite passivation film is formed in negative terminal surface, and the passivation membrane impedance is low, is conducive to the conduction of lithium ion, and battery membrane impedance increase in cyclic process is also smaller, battery capacity decaying is small, but also can significantly improve the hot tank performance and anti-over-charging performance of battery.
Description
Technical field
The application belongs to field of lithium ion battery, specifically, this application involves a kind of nonaqueous electrolytic solution and uses this non-aqueous
The lithium ion battery of electrolyte.
Background technology
Lithium ion battery because have many advantages, such as it is higher than energy, have extended cycle life, self discharge it is small, be widely used in consumer
In electronic product and energy storage and power battery.With the extensive use of lithium ion battery, use environment also tends to be more already
Kind is various, requires the rate of charge, battery life and security performance of battery higher and higher.For example, battery needs urgent charging
In the case of use, more electricity can be possessed in the short time；Battery needs to improve electricity in the case of big multiplying power quick charge
The service life in pond；Battery is required for ensureing that customer's is safe to use during using and overcharge under the high temperature conditions, therefore needs
Improve battery hot tank and anti-over-charging performance.
Rate of charge, service life and the high-temperature storage performance of lithium ion battery are influenced by factors, wherein electrolyte
As the important component of lithium ion battery, there is great influence to it.The power of battery can be improved by electrolyte
Performance is learned, big multiplying power polarization, cyclic process median surface stability, the increasing for reducing positive and negative anodes interface impedance in cyclic process are reduced
Add, to achieve the purpose that improve rate of charge, service life, hot tank and anti-over-charging performance.
Invention content
The primary goal of the invention of the application is to propose a kind of nonaqueous electrolytic solution.
The second goal of the invention of the application is to propose the lithium ion battery using the nonaqueous electrolytic solution.
In order to complete the purpose of the application, the technical solution used for：
A kind of nonaqueous electrolytic solution, including non-aqueous organic solvent, lithium salts and additive, containing such as formula (I) in the additive
Shown in silicon substrate sulfate compound and 3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] alkyl compounds,
Wherein, R1~R6It is each independently selected from hydrogen atom, halogen atom, substituted or unsubstituted C1~20Alkyl, substitution or
Unsubstituted C1~20Alkylene, substituted or unsubstituted C6~26Aryl, substituted or unsubstituted C1~20Alkoxy, substitution do not take
The C in generation6~26Aryloxy group；
Substituent group is selected from halogen, C1~6Alkyl.
Preferably, R1~R6In at least one substituent group be selected from halogen, substituted or unsubstituted C1~12Alkoxy, substitution
Or unsubstituted C1~12Alkyl, substituted or unsubstituted C6~26Aryl.
Preferably, R1~R6In at least one substituent group be selected from halogen, substituted or unsubstituted C1~6Alkoxy, substitution
Or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl.
Preferably, R1~R6For identical group.
Preferably, the silicon substrate sulfate compound is selected from bis- (trimethyl silicon substrate) sulfuric esters, bis- (triethyl group silicon substrate) sulphur
At least one of acid esters, bis- (triphenyl silicon substrate) sulfuric esters, bis- (trifluoro silicon substrate) sulfuric esters.
Preferably, 3, the 9- divinyl -2,4, the structural formula such as formula of 8,10- tetra- oxaspiro [5.5] alkyl compounds
(II) shown in：
Wherein, R21~R30It is each independently selected from hydrogen atom, C1~12Alkyl；
Preferably, R21~R30It is hydrogen atom.
Preferably, mass percentage content of the silicon substrate sulfate compound in nonaqueous electrolytic solution be 0.05%~
3%, preferably 0.1%~2%.
Preferably, 3, the 9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] alkyl compounds are in nonaqueous electrolytic solution
In mass percentage content be 0.01%~3%, preferably 0.1%~2%.
Preferably, the non-aqueous organic solvent is selected from ethylene carbonate, propene carbonate, butylene, fluoro carbonic acid
Vinyl acetate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4-
At least one of butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate；
The lithium salts is selected from lithium hexafluoro phosphate, double trifluoromethanesulfonimide lithiums, bis- (fluorine sulphonyl) imine lithiums, double oxalic acid boron
At least one of sour lithium, difluorine oxalic acid boracic acid lithium.
The application further relates to a kind of lithium ion battery comprising electrolyte, positive plate, negative plate, isolation film and package foil；
The positive plate includes plus plate current-collecting body and the positive diaphragm that is coated on plus plate current-collecting body, negative plate include negative current collector and
The cathode membrane being coated on negative current collector；It is characterized in that, the electrolyte is nonaqueous electrolytic solution described herein.
It includes following aspect that the application, which can reach advantageous effects, but not limited to this：
The application passes through four oxaspiro [5.5] alkyl compounds of 3,9- divinyl -2,4,8,10- and silicon substrate Sulfation
Object synergistic effect is closed, forms stable composite passivation film in negative terminal surface, and the passivation membrane impedance is low, is conducive to the biography of lithium ion
It leads, and battery membrane impedance increase in cyclic process is also smaller, battery capacity decaying is small.And the silicon in silicon substrate sulfuric ester is former
Son is with oxygen atom in 3,9- divinyl -2,4,8,10- four oxaspiro [5.5] alkyl compound easily in electricity in charge and discharge process
The formation of pole interface leads ionic strong silicon-oxygen polymer and carrys out guard electrode material, significantly improves the hot tank performance and anti-over-charging of battery
Performance.
With reference to specific embodiment, the application is expanded on further.It should be understood that these embodiments are merely to illustrate the application
Rather than limitation scope of the present application.
Specific implementation mode
Present invention, which is designed to provide one kind, can significantly provide lithium ion battery rate of charge, improve lithium ion
The nonaqueous electrolytic solution of cycle performance of battery and high-temperature storage performance, and the lithium ion battery using the nonaqueous electrolytic solution is provided.
In order to achieve the above-mentioned object of the invention, this application provides a kind of nonaqueous electrolytic solutions, including non-aqueous organic solvent, lithium salts
And additive, silicon substrate sulfate compound and 3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] alkane are contained in additive
Based compound；
Wherein, shown in the structural formula of silicon substrate sulfate compound such as formula (I)：
Wherein, R1~R6It is each independently selected from hydrogen atom, halogen atom, substituted or unsubstituted C1~20Alkyl, substitution or
Unsubstituted C1~20Alkylene, substituted or unsubstituted C6~26Aryl, substituted or unsubstituted C1~20Alkoxy, substitution do not take
The C in generation6~26Aryloxy group；
Substituent group is selected from halogen, C1~6Alkyl, halogen are selected from F or Cl.
Preferably, R1~R6In at least one substituent group be selected from halogen, substituted or unsubstituted C1~12Alkoxy, substitution
Or unsubstituted C1~12Alkyl, substituted or unsubstituted C6~26Aryl, it is preferred that at least 2 substituent groups are selected from above-mentioned group,
More preferably at least there are 3 substituent groups to be selected from above-mentioned group；
Preferably, R1~R6In at least one substituent group be selected from halogen, substituted or unsubstituted C1~6Alkoxy, substitution
Or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl.
Preferably, R1~R6For identical group.
The preferred upper limit value of the carbon atom number of abovementioned alkyl is followed successively by 16,12,8,6,4,3；For example, in the upper of carbon atom number
In the case that limit value is 16, the carbon atom number range of alkyl refers to 1~16；The most preferably carbon atom number of alkyl is 1~3.Alkyl
Can be alkyl group or naphthenic base：Alkyl group includes straight chained alkyl and the alkyl with branch；Naphthenic base is to contain alicyclic structure
Saturated alkyl can contain or not contain substituent group on alicyclic ring.
As the example of alkyl, can specifically enumerate：It is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, different
Butyl, sec-butyl, tertiary butyl, cyclobutyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, cyclopenta, 2,2- dimethyl propyls,
1- ethyl propyls, 1- methyl butyls, 2- methyl butyls, n-hexyl, isohesyl, 2- hexyls, 3- hexyls, cyclohexyl, 2- methylpents
Base, 3- methyl amyls, 1,1,2- thmethylpropyls, 3,3- dimethylbutyls, n-heptyl, n-octyl, n-nonyl, positive decyl.
The preferred upper limit value of the carbon atom number of above-mentioned alkoxy is followed successively by 16,12,8,6,4,3；For example, in carbon atom number
In the case that upper limit value is 16, the carbon atom number range of alkoxy refers to 1~16；The most preferably carbon atom number of alkoxy be 1~
3.Alkoxy includes unbranched alkoxy and the alkoxy with branch.
As the example of alkyl, can specifically enumerate：Methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy,
Isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, tertiary amoxy, neopentyl oxygen, cyclopentyloxy, 2,2-
Dimethyl propylene oxygroup, 1- ethylpropoxies, 1- methyl butoxies, 2- methyl butoxies, positive hexyloxy, dissident's oxygroup, the own oxygen of 2-
Base, 3- hexyloxies, 2- methyl amoxy, 3- methyl amoxy, 1,1,2- trimethyls propoxyl group, 3,3- dimethyl butyrates oxygroup, just
Heptan oxygroup, n-octyloxy, positive nonyl epoxide, n-decyloxy.
As the example of aryl, can specifically enumerate：Phenyl, naphthalene etc..
Substituent group in the application can be selected from halogen, C1~6Alkyl, the halogen are selected from F or Cl.
Preferably, R1~R6For identical group.That is R1~R6Can be halogen, substituted or unsubstituted C simultaneously1~12Alcoxyl
Base, substituted or unsubstituted C1~12Alkyl, substituted or unsubstituted C6~26Aryl；Preferably, R1~R6It can be simultaneously halogen, take
Generation or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl.
As a kind of improvement of the application nonaqueous electrolytic solution, silicon substrate sulfate compound is selected from bis- (front threes shown in I a of formula
Base silicon substrate) sulfuric ester, bis- (trifluoro silicon substrate) sulfuric esters, formula I shown in bis- (triethyl group silicon substrate) sulfuric esters, I c of formula shown in I b of formula
At least one of (triphenyl silicon substrate) sulfuric esters bis- shown in d：
Wherein, silicon substrate sulfate compound is also selected from least one of following compound：
As a kind of improvement of the application nonaqueous electrolytic solution, 3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] alkane
Shown in the structural formula of based compound such as formula (II)：
Wherein, R21~R30It is each independently selected from hydrogen atom, C1~12Alkyl.
It is further preferred that R21~R30It is each independently selected from hydrogen atom, C1~6Alkyl.
It is further preferred that R23~R30It is hydrogen atom, R23~R30It is each independently selected from hydrogen atom, C1~6Alkyl.
It is furthermore preferred that R21~R30It is hydrogen atom, structural formula is named as divinyl -2 3,9- as shown in II a of formula,
Tetra- oxaspiros of 4,8,10- [5.5] hendecane：
Wherein, 3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] alkyl compounds are also selected from following chemical combination
At least one of object：
As a kind of improvement of the application nonaqueous electrolytic solution, quality of the silicon substrate sulfate compound in nonaqueous electrolytic solution point
Number is 0.05%~3%.This is because when the content of silicon substrate sulfate compound is less than 0.05%, it cannot be in negative terminal surface shape
At complete SEI films, to not can effectively prevent the side reaction caused by the electronics transfer between electrolyte and electrode；And work as silicon
When base sulfate compound content is more than 3%, thicker SEI films can be formed in negative terminal surface, lithium ion mobility resistance is caused to increase
Greatly, it is unfavorable for the cathode interface stability of battery in cyclic process.
It is further preferred that the preferred upper limit of mass fraction range of the silicon substrate sulfate compound in nonaqueous electrolytic solution according to
Secondary is 2.8%, 2.5%, 2.0%, 1.5%, 1.0%, preferred lower limit is followed successively by 0.08%, 0.1%, 0.3%, 0.5%,
0.6%.It is further preferred that mass fraction of the silicon substrate sulfate compound in nonaqueous electrolytic solution is 0.1%~2%.
As a kind of improvement of the application nonaqueous electrolytic solution, 3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] alkane
Mass fraction of the based compound in nonaqueous electrolytic solution is 0.01%~3%.This is because work as divinyl -2,4,8 3,9-,
When the additive amount of tetra- oxaspiros of 10- [5.5] alkyl compound in the electrolytic solution is less than 0.01%, it is impossible to be effectively formed stabilization
SEI films, the cycle performance of battery is without improvement；And work as 3,9- divinyl -2,4,8,10- four oxaspiro [5.5] alkyl chemical combination
When the content of object is higher than 3%, the viscosity of electrolyte is increased, the migration of lithium ion is slowed down.It is further preferred that 3,9- divinyls
Mass fraction of four oxaspiros of base -2,4,8,10- [5.5] alkyl compound in nonaqueous electrolytic solution is 0.1%~2%.
As a kind of improvement of the application nonaqueous electrolytic solution, non-aqueous organic solvent is that carbon atom number is 1~8 and containing extremely
The compound of a few ester group.
As a kind of improvement of the application nonaqueous electrolytic solution, non-aqueous organic solvent be selected from ethylene carbonate, propene carbonate,
Butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbonic acid first
In propyl ester, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate extremely
Few one kind.
As a kind of improvement of the application nonaqueous electrolytic solution, lithium salts is optionally from least one in organic lithium salt or inorganic lithium salt
Kind.
As a kind of improvement of the application nonaqueous electrolytic solution, in lithium salts containing in fluorine element, boron element, P elements at least
It is a kind of.
As a kind of improvement of the application nonaqueous electrolytic solution, lithium salts is selected from lithium hexafluoro phosphate LiPF6, double fluoroform sulphurs
Imide li LiN (CF3SO2)2(being abbreviated as LiTFSI), bis- (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (being abbreviated as LiFSI),
Di-oxalate lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4) in (being abbreviated as LiDFOB)
At least one.
In order to achieve the above-mentioned object of the invention, present invention also provides a kind of lithium ion batteries comprising electrolyte, anode
Piece, negative plate, isolation film and package foil；The positive plate includes plus plate current-collecting body and the anode that is coated on plus plate current-collecting body
Diaphragm, negative plate include negative current collector and the cathode membrane that is coated on negative current collector；The electrolyte is any of the above-described
Nonaqueous electrolytic solution described in paragraph.
As a kind of improvement of the application lithium ion battery, it is described anode diaphragm include positive electrode active materials, binder and
Conductive agent.
As a kind of improvement of the application lithium ion battery, positive electrode active materials are optionally from cobalt acid lithium LiCoO2, lithium nickel manganese
The mixing of at least one of cobalt ternary material, LiFePO 4, LiMn2O4 or cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material
Object.
As a kind of improvement of the application lithium ion battery, cathode membrane includes negative electrode active material, binder and conduction
Agent.
As a kind of improvement of the application lithium ion battery, negative electrode active material is graphite and/or silicon.
It is with reference to embodiments, right in order to make present invention purpose, technical solution and technique effect be more clear
The application is further elaborated.It should be understood that embodiment described in this specification is merely to explain this Shen
Please, it is not intended to limit the application.
Examples 1 to 10
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, ethylene carbonate (is abbreviated as
EC), diethyl carbonate (being abbreviated as DEC), propene carbonate (being abbreviated as PC), ethyl propionate, fluorinated ethylene carbonate (are write a Chinese character in simplified form
For FEC) according to 20:30:20:25:5 mass ratio after mixing, obtains nonaqueous solvents, then the lithium salts that will fully dry
LiPF6It is dissolved in above-mentioned nonaqueous solvents, is made into LiPF6The basic electrolyte of a concentration of 1mol/L.
Shown in table 1, silicon substrate sulfate compound (I a, I b, I c, I d) and 3,9- bis- are added in basic electrolyte
Four oxaspiros of vinyl -2,4,8,10- [5.5] hendecane compound (II a).
The preparation of lithium ion battery：
1) preparation of positive plate：By positive active material cobalt acid lithium (molecular formula LiCoO2), conductive agent acetylene black, bonding
Agent polyvinylidene fluoride (being abbreviated as PVDF) is by weight 96:2:2 in suitable N-Methyl pyrrolidone (being abbreviated as NMP) solvent
In be thoroughly mixed, form it into uniform anode sizing agent；This slurry is coated on plus plate current-collecting body Al foils, dries, is cold
Pressure, obtains positive plate.
2) preparation of negative plate：Negative electrode active material graphite, conductive agent acetylene black, binder butadiene-styrene rubber (are abbreviated as
SBR), thickener sodium carboxymethylcellulose (being abbreviated as CMC) is according to weight ratio 95:2:2:1 in suitable deionized water solvent
It is thoroughly mixed, forms it into uniform negative electrode slurry；This slurry is coated on negative current collector Cu foils, drying, cold pressing,
Obtain negative plate.
3) isolation film：Using PE porous polymer films as isolation film.
4) preparation of lithium ion battery：Positive plate, isolation film, negative plate are folded in order, isolation film is made to be in positive and negative
Play the role of isolation between pole piece, then winding obtains naked battery core；Naked battery core is placed in outer packing foil, is prepared above-mentioned
Electrolyte be injected into it is dry after battery in, by processes such as Vacuum Package, standing, chemical conversion, shapings, that is, complete lithium-ion electric
The preparation in pond.
Comparative example 1~6
Basic electrolyte is prepared according to the method for embodiment 1, comparative example 1 is not added additive, is electrolysed in comparative example 2~3
Solution additive and respective additive amount are as shown in table 1.
Examples 1 to 8 and electrolysis additive in comparative example 1~6 and respective additive amount are as shown in table 1.
Table 1：Electrolysis additive combination in each comparative example and embodiment and additive amount
Lithium ion battery made from each comparative example of the application and embodiment will be tested for the property by experiment below.
Test one, loop test
The lithium ion battery being prepared respectively is subjected to following tests：
At 25 DEG C, by lithium ion battery, with 1C constant-current charges to 4.4V, then constant-voltage charge to electric current is 0.05C, then
, according to above-mentioned condition into the so many secondary cycle charging/electric discharge of places, divided at this time to recycle for the first time with 1C constant-current discharges to 3.0V
Be not calculated lithium ion battery recycle 50 times, 100 times, 200 times, 300 times and 500 times after capacity retention ratio, every group each 5
Battery, wherein the capacity retention ratio after cycle is calculated according to the following formula.In each lithium ion battery selected electrolyte with
And obtained relevant test data is referring to table 3.
Capacity retention ratio after cycle=(discharge capacity of corresponding cycle/discharge capacity recycled for the first time) × 100%, it follows
The results are shown in Table 2 for ring test.
Table 2：Capacity retention ratio test result after cycle
| Group | 50 times | 100 times | 200 times | 300 times | 500 times |
| Embodiment 1 | 98.2% | 95.9% | 94.1% | 91.8% | 87.3% |
| Embodiment 2 | 97.5% | 95.5% | 93.7% | 91.4% | 86.5% |
| Embodiment 3 | 97.4% | 95.3% | 93.4% | 91.3% | 85.9% |
| Embodiment 4 | 97.1% | 94.8% | 93.3% | 91.0% | 85.8% |
| Embodiment 5 | 96.4% | 93.8% | 92.2% | 88.3% | 84.0% |
| Embodiment 6 | 96.4% | 93.6% | 91.1% | 86.5% | 82.3% |
| Embodiment 7 | 97.4% | 93.4% | 91.8% | 86.6% | 82.8% |
| Embodiment 8 | 96.3% | 92.2% | 89.1% | 86.2% | 80.1% |
| Embodiment 9 | 95.3% | 90.2% | 85.1% | 80.2% | 74.1% |
| Embodiment 10 | 95.1% | 89.2% | 84.5% | 79.0% | 73.1% |
| Comparative example 1 | 95.3% | 91.5% | 83.5% | 73.7% | 62.7% |
| Comparative example 2 | 96.2% | 93.1% | 87.4% | 79.2% | 70.6% |
| Comparative example 3 | 95.0% | 92.2% | 85.6% | 77.5% | 68.8% |
| Comparative example 4 | 95.8% | 92.5% | 86.4% | 78.9% | 69.2% |
| Comparative example 5 | 95.8% | 92.5% | 87.4% | 79.4% | 67.0% |
| Comparative example 6 | 95.9% | 91.4% | 83.5% | 74.3% | 61.3% |
It can be seen that compared with comparative example 1 in conjunction in Tables 1 and 2,2% be individually added into the electrolyte of comparative example 2~3
3,9- divinyl -2,4, when 8,10- tetra- oxaspiro [5.5] hendecanes or 2% silicon substrate sulfate compound, lithium ion battery
Cycle performance slightly improves.In Examples 1 to 10,3, the 9- divinyl-that mass fraction is 1% is added in electrolyte simultaneously
When the silicon substrate sulfate compound that 2,4,8,10- tetra- oxaspiro [5.5] hendecanes and mass fraction are 1%, the cyclicity of battery
It can be obviously improved.However, 3,9- divinyl -2,4 in the electrolyte, 8,10- tetra- oxaspiro [5.5] hendecanes be more than 3% or
When the content of 3,4- ethylene dialkoxy thiophene compounds is more than 3%, not only the cycle performance of battery does not improve, or even can dislike
Change, 4%3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] hendecanes and 4% silicon substrate sulphur are especially added in electrolyte
The cycle conservation rate of the comparative example 6 of ester compound, battery is far below other groups.
Hot tank test after test two, cycle
The battery after 500 25 DEG C of cycles will be carried out, with 0.5C electric currents constant-current charge to 4.4V at 25 DEG C, 4.4V is permanent
It is 0.025C that pressure, which charges to electric current, is at 4.4V fully charged states, then battery is placed in 150 DEG C of high temperature furnace and keeps 1
Hour, the state of battery after observation test.
Recycling rear hot box test, the results are shown in Table 3.
Table 3：Recycle rear hot box test result
| Group | Hot tank is tested |
| Embodiment 1 | 5/5OK |
| Embodiment 2 | 5/5OK |
| Embodiment 3 | 5/5OK |
| Embodiment 4 | 5/5OK |
| Embodiment 5 | 5/5OK |
| Embodiment 6 | 5/5OK |
| Embodiment 7 | 5/5OK |
| Embodiment 8 | 5/5OK |
| Embodiment 9 | 5/5OK |
| Embodiment 10 | 5/5OK |
| Comparative example 1 | 5/5fire |
| Comparative example 2 | 1/5OK,4/5fire |
| Comparative example 3 | 1/5OK,4/5fire |
| Comparative example 4 | 1/5OK,4/5fire |
| Comparative example 5 | 1/5OK,4/5fire |
| Comparative example 6 | 5/5fire |
It can be seen that when 3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] hendecanes in conjunction in table 1 and table 3
When closing the content of object higher than 3%, it will the test of battery hot tank is caught fire after leading to cycle, and it is because excessive that reason, which can be considered,
3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] hendecanes membrane impedance in cyclic process increase, and battery is caused to follow
Lithium metal is precipitated during ring, deteriorates the thermal stability of battery cathode, deteriorates the hot tank performance after circulating battery.In contrast,
The composite passivation film that silicon substrate sulfate compound is formed is added in electrolyte has preferable heat resistance, improves battery after cycle
Hot tank performance.Therefore, silicon substrate sulfate compound and 3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] hendecanes are made
It arranges in pairs or groups simultaneously in use, the hot tank performance of battery after cycling can be significantly improved for electrolysis additive.
Test three, anti-over-charging test
The battery for partly filling state is discharged to 3.0V at 25 DEG C with 0.5C, then permanent with 0.4C constant-current charges to 10V, then 10V
Pressure charging 2h, observes the state of battery.
The results are shown in Table 4 for anti-over-charging test.
Table 4：Anti-over-charging test result
| Group | Anti-over-charging is tested |
| Embodiment 1 | 5/5OK |
| Embodiment 2 | 5/5OK |
| Embodiment 3 | 5/5OK |
| Embodiment 4 | 5/5OK |
| Embodiment 5 | 5/5OK |
| Embodiment 6 | 5/5OK |
| Embodiment 7 | 5/5OK |
| Embodiment 8 | 5/5OK |
| Embodiment 9 | 5/5OK |
| Embodiment 10 | 5/5OK |
| Comparative example 1 | 5/5fire |
| Comparative example 2 | 1/5OK,4/5fire |
| Comparative example 3 | 1/5OK,4/5fire |
| Comparative example 4 | 1/5OK,4/5fire |
| Comparative example 5 | 1/5OK,4/5fire |
| Comparative example 6 | 5/5fire |
It can be seen that when 3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] hendecanes in conjunction in table 1 and table 4
When closing the content of object higher than 3%, it will cause battery to catch fire during anti-over-charging, it is because excessive that reason, which can be considered,
3,9- divinyl -2,4,8,10- tetra- oxaspiro [5.5] hendecanes in lasting charging process membrane impedance increase, lead to gold
Belong to lithium to be precipitated, lasting lithium easily leads to battery short circuit, cells burst in negative terminal surface deposition.In contrast, it is added in electrolyte
Silicon substrate sulfate compound can form stable and low impedance composite passivation film, which is not easy in lasting charging process
It is destroyed, therefore is not easy to form micro-short circuit, so as to improve battery anti-over-charging performance.Therefore, silicon substrate sulfate compound and 3,9-
Divinyl -2,4,8,10- tetra- oxaspiro [5.5] hendecanes are arranged in pairs or groups in use, can be notable simultaneously as electrolysis additive
Improve the anti-over-charging performance of battery.
By all of above description it is found that the application is not higher than 3% by the way that mass fraction is added simultaneously in the electrolytic solution
Four oxaspiro [5.5] hendecanes of 3,9- divinyl -2,4,8,10- and mass fraction are not higher than 3% silicon substrate sulfuric ester chemical combination
Object can significantly improve rate of charge, service life, anti-over-charging and the cycle rear hot box performance of lithium ion battery.
Embodiment 11~18
Basic electrolyte is prepared according to the method for embodiment 1, the composition for differing only in additive is different, specific such as table 5
It is shown.
Table 5：Electrolysis additive combination in embodiment 11~18 and additive amount
Capacity retention ratio after the cycle for the basic electrolyte being prepared by embodiment 11~18, the hot tank after cycle are surveyed
Test result and anti-over-charging test result are similar to the test result of Examples 1 to 10.
According to the disclosure and teachings of the above specification, the application those skilled in the art can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the application is not limited to specific implementation mode disclosed and described above, to this
Some modifications and changes of application should also be as falling into the protection domain of claims hereof.In addition, although this specification
In used some specific terms, these terms are merely for convenience of description, not to the application constitute any restrictions.
Claims (11)
1. a kind of nonaqueous electrolytic solution, including non-aqueous organic solvent, lithium salts and additive, which is characterized in that contain in the additive
Just like silicon substrate sulfate compound shown in formula (I) and 3,9- divinyl -2,4,8,10- four oxaspiro [5.5] alkyl chemical combination
Object,
Wherein, R1~R6It is each independently selected from hydrogen atom, halogen atom, substituted or unsubstituted C1~20Alkyl, substitution do not take
The C in generation1~20Alkylene, substituted or unsubstituted C6~26Aryl, substituted or unsubstituted C1~20It is alkoxy, substituted or unsubstituted
C6~26Aryloxy group；
Substituent group is selected from halogen, C1~6Alkyl,
Mass percentage content of the silicon substrate sulfate compound in nonaqueous electrolytic solution is 0.05%~3%, and described
Mass percentage content of 3,9- divinyl -2,4,8,10- four oxaspiro [5.5] alkyl compound in nonaqueous electrolytic solution be
0.01%~3%.
2. nonaqueous electrolytic solution according to claim 1, which is characterized in that R1~R6In at least one be selected from halogen, substitution
Or unsubstituted C1~12Alkoxy, substituted or unsubstituted C1~12Alkyl, substituted or unsubstituted C6~26Aryl.
3. nonaqueous electrolytic solution according to claim 1, which is characterized in that R1~R6In at least one be selected from halogen, substitution
Or unsubstituted C1~6Alkoxy, substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl.
4. nonaqueous electrolytic solution according to claim 2 or 3, which is characterized in that R1~R6For identical group.
5. nonaqueous electrolytic solution according to claim 4, it is characterised in that：The silicon substrate sulfate compound is selected from bis- (three
Methylsilyl) sulfuric ester, bis- (triethyl group silicon substrate) sulfuric esters, bis- (triphenyl silicon substrate) sulfuric esters, bis- (trifluoro silicon substrate) sulfuric esters
At least one of.
6. nonaqueous electrolytic solution according to claim 1, which is characterized in that 3, the 9- divinyl -2,4,8,10- tetra- oxygen
Shown in the structural formula such as formula (II) of miscellaneous spiral shell [5.5] alkyl compound：
Wherein, R21~R30It is each independently selected from hydrogen atom, C1~12Alkyl.
7. nonaqueous electrolytic solution according to claim 6, which is characterized in that
R21~R30It is hydrogen atom.
8. nonaqueous electrolytic solution according to claim 1, which is characterized in that the silicon substrate sulfate compound is in non-aqueous solution electrolysis
Mass percentage content in liquid is 0.1%~2%.
9. nonaqueous electrolytic solution according to claim 1, which is characterized in that 3, the 9- divinyl -2,4,8,10- tetra- oxygen
Mass percentage content of miscellaneous spiral shell [5.5] alkyl compound in nonaqueous electrolytic solution is 0.1%~2%.
10. nonaqueous electrolytic solution according to claim 1, which is characterized in that the non-aqueous organic solvent is selected from ethylene carbonate
Ester, propene carbonate, butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid
Dipropyl, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate,
At least one of ethyl butyrate；
The lithium salts is selected from lithium hexafluoro phosphate, double trifluoromethanesulfonimide lithiums, bis- (fluorine sulphonyl) imine lithiums, double oxalic acid boric acid
At least one of lithium, difluorine oxalic acid boracic acid lithium.
11. a kind of lithium ion battery comprising electrolyte, positive plate, negative plate, isolation film and package foil；
The positive plate includes plus plate current-collecting body and the positive diaphragm that is coated on plus plate current-collecting body, and negative plate includes negative pole currect collecting
Body and the cathode membrane being coated on negative current collector；It is characterized in that, the electrolyte is any one of claim 1~10
The nonaqueous electrolytic solution.
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| CN108242565B (en) * | 2016-12-26 | 2020-08-25 | 比亚迪股份有限公司 | Electrolyte, negative electrode and lithium ion battery |
| CN108242557B (en) * | 2016-12-26 | 2020-08-28 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN109428112B (en) * | 2017-08-23 | 2020-12-18 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electrolyte thereof |
| KR20190027188A (en) | 2017-09-06 | 2019-03-14 | 삼성에스디아이 주식회사 | Non-electrolyte for rechargeable lithium battery and rechargeable lithium battery including same |
| KR102449844B1 (en) * | 2017-09-06 | 2022-09-29 | 삼성에스디아이 주식회사 | Rechargeable lithium battery and rechargeable lithium battery including same |
| JP7137755B2 (en) * | 2018-09-19 | 2022-09-15 | トヨタ自動車株式会社 | Non-aqueous electrolyte for lithium-ion secondary batteries |
| CN110474088A (en) * | 2019-08-15 | 2019-11-19 | 天津市捷威动力工业有限公司 | A kind of ternary high-voltage lithium-ion battery electrolyte |
| CN112467215A (en) * | 2020-11-30 | 2021-03-09 | 远景动力技术(江苏)有限公司 | Electrolyte and lithium ion battery |
| CN115189021A (en) * | 2021-04-07 | 2022-10-14 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101606264A (en) * | 2007-02-16 | 2009-12-16 | Sk能源株式会社 | The preparation method of lithium secondary battery |
| CN104600362A (en) * | 2015-02-05 | 2015-05-06 | 深圳市三讯电子有限公司 | Power battery and lithium ion electrolyte thereof |
Family Cites Families (2)
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| US8877390B2 (en) * | 2010-05-25 | 2014-11-04 | Uchicago Argonne, Llc | Redox shuttles for lithium ion batteries |
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2016
- 2016-03-28 CN CN201610183641.4A patent/CN105655640B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101606264A (en) * | 2007-02-16 | 2009-12-16 | Sk能源株式会社 | The preparation method of lithium secondary battery |
| CN104600362A (en) * | 2015-02-05 | 2015-05-06 | 深圳市三讯电子有限公司 | Power battery and lithium ion electrolyte thereof |
Cited By (1)
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