CN114512721B - Non-aqueous electrolyte of lithium ion battery and lithium ion battery - Google Patents
Non-aqueous electrolyte of lithium ion battery and lithium ion battery Download PDFInfo
- Publication number
- CN114512721B CN114512721B CN202210149798.0A CN202210149798A CN114512721B CN 114512721 B CN114512721 B CN 114512721B CN 202210149798 A CN202210149798 A CN 202210149798A CN 114512721 B CN114512721 B CN 114512721B
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- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- lithium
- nonaqueous electrolyte
- equal
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 82
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 39
- -1 alkenyl siloxane compound Chemical class 0.000 claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 238000009831 deintercalation Methods 0.000 claims description 7
- 238000009830 intercalation Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-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
- MVKYQTGCKJXECD-UHFFFAOYSA-N ethane-1,2-diol;prop-1-ene Chemical group CC=C.CC=C.OCCO MVKYQTGCKJXECD-UHFFFAOYSA-N 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910010199 LiAl Inorganic materials 0.000 claims description 2
- 229910013733 LiCo Inorganic materials 0.000 claims description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 2
- 229910013391 LizN Inorganic materials 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- 150000001408 amides Chemical class 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- XUEXTJJSYQHTTC-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=C)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=C)O[Si](C=2C=CC=CC=2)(C=C)O[Si]1(C=C)C1=CC=CC=C1 XUEXTJJSYQHTTC-UHFFFAOYSA-N 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 28
- 238000011084 recovery Methods 0.000 abstract description 19
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- MWNWHRXJMMENND-UHFFFAOYSA-M sodium;4,6-bis(sulfanylidene)-1h-1,3,5-triazine-2-thiolate Chemical compound [Na+].[S-]C1=NC(=S)NC(=S)N1 MWNWHRXJMMENND-UHFFFAOYSA-M 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N thianaphthalene Natural products C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-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
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- LNLFLMCWDHZINJ-UHFFFAOYSA-N hexane-1,3,6-tricarbonitrile Chemical compound N#CCCCC(C#N)CCC#N LNLFLMCWDHZINJ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lithium ion battery nonaqueous electrolyte and a lithium ion battery. The invention utilizes the alkenyl siloxane compound with a cyclic structure and the boroxine compound with a cyclic structure to be added into the electrolyte, can form stable SEI films on the surfaces of the anode and cathode electrode materials, and can keep good long-cycle stability, storage capacity retention rate and recovery rate and smaller volume expansion of the battery under a high-temperature environment.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a non-aqueous electrolyte of a lithium ion battery and the lithium ion battery.
Background
The improvement of the battery voltage is one of important methods for improving the energy density of the battery, but the problem of battery performance caused by high voltage is also very prominent, for example, the problem that the battery is easy to collapse in a negative electrode structure to cause lithium precipitation of the battery, transition metal ions are dissolved out to catalyze electrolyte to decompose and produce gas, and the problem that the crystal structure collapses due to oxygen release of a positive electrode can influence the long-cycle performance and the storage performance of the battery.
CN109755648A discloses an electrolyte, which can significantly improve the safety performance, storage performance and cycle performance of a battery under high voltage conditions by adding benzothiophene compound and trialkoxyboroxine to act synergistically; the trialkoxy boroxine can form a film on the anode preferentially, so that the anode is effectively protected, meanwhile, boron atoms in the trialkoxy boroxine can coordinate with oxygen atoms in a cathode material to play a role in protecting the cathode, the cathode material is further protected, a benzothiophene compound forms a film on the anode, and the storage performance and the cycle performance of the electrolyte under the high-voltage condition are obviously improved by the synergistic effect of the trialkoxy boroxine and the anode. However, this invention cannot complex the metal ions eluted from the positive electrode, and has a cycle performance of only 100 weeks, and cannot suppress capacity fade of the long-cycle battery.
Accordingly, in the art, it is desired to develop a material capable of solving battery safety problems caused by excessive capacity retention rate and recovery rate decay in high-temperature storage of a high-voltage lithium ion battery, excessive high-temperature long-cycle capacity decay, and volume expansion in a high-temperature environment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a non-aqueous electrolyte of a lithium ion battery and the lithium ion battery, in particular to a non-aqueous electrolyte of a high-voltage lithium ion battery and the lithium ion battery. The non-aqueous electrolyte of the lithium ion battery is suitable for high-voltage lithium ion batteries, can solve the problems of battery safety caused by overlarge capacity retention rate and recovery rate attenuation in high-temperature storage of the conventional high-voltage lithium ion battery, overlarge high-temperature long-cycle capacity attenuation and volume expansion in a high-temperature environment, and particularly can show excellent electrochemical performance in a high-energy-density silicon-carbon/silicon-oxygen negative electrode material battery or a high-nickel high-voltage battery system.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in one aspect, the present invention provides a lithium ion battery nonaqueous electrolyte comprising a lithium salt electrolyte, a nonaqueous solvent, and an additive comprising at least one cyclic alkenylsiloxane compound having a structure represented by formula (1) and at least one cyclic boroxine compound having a structure represented by formula (2):
wherein R is 1 Selected from hydrogen, halogen, cyano, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C6-C30 aryl, amide, phosphate, sulfonyl, siloxy or borate, n is an integer from 3 to 10 (e.g., 3, 4, 5, 6, 7, 8, 9 or 10); r is R 2 Selected from hydrogen, halogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C6-C30 aryl, m is an integer from 3 to 10 (e.g., 3, 4, 5, 6, 7, 8, 9, or 10).
In the present invention, the C1-C5 alkyl group may be a C1, C2, C3, C4 or C5 alkyl group.
The aryl of C6-C30 may be a C6, C8, C10, C12, C16, C18, C20, C22, C24, C26, C28 or C29 aryl.
Preferably, where a group as defined above is a substituted said group, the substituent is selected from at least one of halogen, C1-C6 (e.g. C1, C2, C3, C4, C5 or C6) alkyl or C1-C6 (e.g. C1, C2, C3, C4, C5 or C6) alkoxy.
In the present invention, the inventors found that the key means for solving the problem is: when the cyclic alkenylsiloxane compound of formula (1) and the cyclic boroxine compound of formula (2) are combined in the electrolyte, a stable solid electrolyte interface film can be formed on the surface of the positive electrode and the negative electrode of the lithium ion battery, the interface film has excellent ion conductivity, the lithium ion impedance is reduced, the capacity retention rate and the recovery rate are high in a high-temperature storage environment, the capacity attenuation speed is reduced in the charging and discharging process, and the volume expansion of the battery is restrained in the high-temperature environment.
The cyclic alkenylsiloxane compound of formula (1) and the cyclic boroxine compound of formula (2) are combined in the electrolyte, although no theory proves the mechanism of electrochemical stability of the compound at present, the inventor can reasonably speculate that: the double bonds in the formula (1) are broken at the initial stage of the electrochemical reaction process, a compact solid electrolyte interface film can be formed at the positive electrode and the negative electrode, meanwhile, the formula (2) can also participate in film formation in an open loop mode, the ion compact stability of the interface film is enhanced, the interface film cannot be damaged under the high-voltage high-temperature condition, and further, consumed active lithium ions are fewer, so that the capacity of the high-voltage lithium ion battery is ensured. Meanwhile, the Si-O-bond can complex metal ions dissolved out by the anode, so that the catalytic reaction of the metal ions on the electrolyte is further reduced, si atoms are easy to adsorb fluoride ions, and the decomposition of lithium salt is inhibited; the B atoms can coordinate with oxygen atoms in the positive electrode material to stabilize the crystal structure of the positive electrode material and protect the stability of the positive electrode in the charge and discharge process.
Preferably, the cyclic alkenyl siloxane compound having the structure shown in formula (1) is any one of 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinyl cyclotetrasiloxane (abbreviated as TTCS), 2,4,6, 8-octa (vinyl) -1,3,5,7,2,4,6,8-tetraoxatetrasiloxane (abbreviated as ots), tetramethyl-tetravinyl cyclotetrasiloxane (abbreviated as ViD) or tetraethylene-tetraphenyl cyclotetrasiloxane (abbreviated as TMTPS).
Preferably, the cyclic borane compound having the formula (2) is any one of the following compounds:
preferably, the content of the cyclic alkenylsiloxane compound having the structure represented by formula (1) is 0.01 to 5% (e.g., 0.01%, 0.05%, 1%, 3% or 5%) and the content of the cyclic boroxine compound having the structure represented by formula (2) is 0.01 to 5% (e.g., 0.01%, 0.05%, 1%, 3% or 5%) based on 100% of the total mass of the nonaqueous electrolyte solution for a lithium ion battery.
Preferably, the additive further comprises other additives including one or a combination of at least two of lithium difluorophosphate, vinyl sulfate, fluoroethylene carbonate, 1, 3-propane sultone, ethylene glycol dipropylene nitrile ether, 1,3, 6-hexane tri-nitrile, succinonitrile, adiponitrile, lithium difluorobis-oxalato phosphate or 1,2, 3-tetrafluoroethyl-2, 3-tetrafluoropropyl ether.
Preferably, the content of the other additive is 0.01 to 25%, for example 0.01%, 0.05%, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 20%, 22% or 25%, based on 100% of the total mass of the nonaqueous electrolyte solution for lithium ion batteries.
Preferably, the lithium salt electrolyte comprises any one or a combination of at least two of lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis-fluorosulfonyl imide, or lithium bis-trifluoromethanesulfonyl imide.
Preferably, the content of the lithium salt electrolyte is 2 to 25%, for example 3%, 5%, 8%, 10%, 13%, 15%, 20%, 22% or 25%, based on 100% of the total mass of the lithium ion battery nonaqueous electrolyte.
Preferably, the nonaqueous solvent is one or a combination of at least two of ethylene glycol diethyl ether, methyl propionate (abbreviated as MP), methyl acetate (abbreviated as MA), propyl propionate (abbreviated as PP), methyl butyrate (abbreviated as MB), ethyl butyrate (abbreviated as EB), propyl acetate (abbreviated as PA), butyl butyrate (abbreviated as BB), acetonitrile (abbreviated as AN), methyl propyl carbonate (abbreviated as MPC), ethyl propionate (abbreviated as EP), gamma-butyrolactone (abbreviated as GBL), sulfolane (abbreviated as SL), dimethyl sulfoxide, tetrahydrofuran, propylene carbonate (abbreviated as PC), ethyl acetate (abbreviated as EA), diethyl carbonate (abbreviated as DEC), methyl ethyl carbonate (abbreviated as EMC), dimethyl carbonate (abbreviated as DMC), and ethylene carbonate (abbreviated as EC).
Preferably, the nonaqueous solvent is contained in an amount of 40 to 92.98%, for example, 40%, 43%, 45%, 48%, 50%, 55%, 58%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 92% based on 100% of the total mass of the nonaqueous electrolyte for lithium ion batteries.
In another aspect, the invention also provides a lithium ion battery, which comprises the lithium ion battery nonaqueous electrolyte.
In the invention, the lithium ion battery comprises a battery shell, an electric core and the lithium ion battery nonaqueous electrolyte, wherein the electric core and the lithium ion battery nonaqueous electrolyte are sealed in the battery shell.
Preferably, the battery cell includes a positive electrode, a negative electrode, and a separator or a solid electrolyte layer disposed between the positive electrode and the negative electrode.
Preferably, the positive electrode includes an active material capable of intercalating and deintercalating lithium, and the active material capable of intercalating and deintercalating lithium is preferably a lithium transition metal composite oxide.
Preferably, the negative electrode includes a metal or alloy capable of intercalating and deintercalating lithium or forming an alloy with lithium or a metal oxide capable of intercalating/deintercalating lithium.
Preferably, the active material capable of intercalating and deintercalating lithium is LiNi x Co y Mn z L (1-x-y-z) O 2 、LiCo x' L (1-x') O2、LiNi x” L' y' Mn (2-x”-y') O 4 、Li z' MPO 4 、LiMn 2 O 4 At least one of (a) and (b); wherein L is at least one of Al, sr, mg, ti, ca, zr, zn, si, fe; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x+y+z is more than or equal to 0 and less than or equal to 1, x ' is more than or equal to 0 and less than or equal to 0.6, y ' is more than or equal to 0.01 and less than or equal to 0.2, and L ' is at least one of Co, al, sr, mg, ti, ca, zr, zn, si or Fe; and z' is more than or equal to 0.5 and less than or equal to 1, and M is at least one of Fe, mn or Co.
Preferably, the material of the negative electrode comprises crystalline carbon, lithium metal, siO 2 Graphite composite, siC/graphite composite, liMnO 2 、LiAl、Li 3 Sb、Li 3 Cd、LiZn、Li 3 Bi、Li 4 Si、Li 4.4 Pb、Li 4.4 Sn、LiC 6 、Li 3 FeN 2 、Li 2.6 CoN 0.4 、Li 2.6 CuN 0.4 Or Li (lithium) 4 Ti 5 O 12 At least one of them.
Preferably, the lithium ion battery of the present invention has a charge cutoff voltage of not less than 3.6V, for example, 3.6V, 4.0V, 4.5V, 4.8V, 5.0V, etc.
Preferably, the working voltage of the lithium ion battery is 3.6V to 5V, for example, 3.6V, 4.0V, 4.5V, 4.8V, 5.0V, and preferably 4.35V to 4.8V.
Compared with the prior art, the invention has the following beneficial effects:
the invention utilizes the alkenyl siloxane compound with a cyclic structure and the boroxine compound with a cyclic structure to be added into the electrolyte, can form stable SEI films on the surfaces of the anode and cathode electrode materials, can keep good long-cycle stability, storage capacity retention rate and recovery rate and small volume expansion of the battery under a high-temperature environment, and can be cycled for 600 times at 45 ℃ for more than 91 percent, stored for 14 days at 60 ℃, the capacity retention rate is more than 90 percent, the capacity recovery rate is more than 91 percent and the volume expansion rate is less than 4.8 percent.
Drawings
FIG. 1 is a graph showing the results of the test of capacity retention of the batteries of examples 1-2 and comparative examples 1-2 at a high temperature of 45℃for 600 weeks;
FIG. 2 is a graph showing the results of testing the capacity retention and recovery of the batteries of examples 1-2 and comparative examples 1-2 when stored at 60℃for 14 days;
FIG. 3 is a graph showing the results of the test of the volume increase rate of the batteries of examples 1-2 and comparative examples 1-2 stored at a high temperature of 60℃for 14 days.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present example provides a high-voltage lithium ion battery nonaqueous electrolyte comprising additives of 14.5% by mass of lithium hexafluorophosphate, 21.0% by mass of EC, 10.0% by mass of PC and 38.0% by mass of a nonaqueous solvent of PP, 5.00% by mass of 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinyl cyclotetrasiloxane (TTCS, commercially available from shanghai-terra-chemical industry development limited), 1.50% by mass of a cyclic borane compound B01 (commercially available from santa chemical industry limited), 9.00% by mass of fluoroethylene carbonate (commercially available from Jiangsu-hua materials sciences limited), and 1.00% by mass of ethylene sulfate (commercially available from santa chemical industry limited).
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps:
the electrolyte is prepared in a glove box, the nitrogen content in the glove box is 99.999 percent, the actual oxygen content in the glove box is less than 2ppm, and the moisture content is less than 0.1ppm. Based on 100% of the total mass of the nonaqueous electrolyte, 21.0% of EC, 10.0% of PC and 38.0% of PP battery grade organic solvent are uniformly mixed, and then 14.5% of lithium hexafluorophosphate which is fully dried is added into the nonaqueous solvent, 5.00% of 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinyl cyclosiloxane and 1.50% of B01 are added, and 9.00% of fluoroethylene carbonate and 1.00% of ethylene sulfate are added to prepare the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
preparing a positive electrode: liCoO is added with 2 Mixing powder, binder polyvinylidene fluoride (PVDF) and conductive agent acetylene black according to the weight ratio of 97.5:1.5:1.5, adding N-methyl pyrrolidone (NMP), and stirring under the action of a vacuum stirrer until the mixed system becomes anode slurry with uniform fluidity; uniformly coating the anode slurry on an aluminum foil with the thickness of 15 mu m; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 15 mu m by the coating; and baking the coated aluminum foil in 5 sections of ovens with different temperature gradients, drying the aluminum foil in an oven with the temperature of 120 ℃ for 8 hours, and rolling and slitting the aluminum foil to obtain the required positive plate.
Preparing a negative electrode: preparing a graphite negative electrode material with the mass ratio of 95.7wt%, a conductive carbon black (SP) conductive agent with the mass ratio of 1wt%, a sodium carboxymethyl cellulose (CMC) dispersing agent with the mass ratio of 1.3wt% and a Styrene Butadiene Rubber (SBR) binder with the mass ratio of 2wt% into a negative electrode slurry by a wet process; uniformly coating the negative electrode slurry on a copper foil with the thickness of 15 mu m; and baking the coated copper foil in 5 sections of ovens with different temperature gradients, drying the copper foil in an oven with the temperature of 85 ℃ for 5 hours, and rolling and slitting the copper foil to obtain the required graphite negative electrode sheet.
Preparation of a diaphragm: the PE porous polymer film with the thickness of 7-9 mm is used as a diaphragm.
Preparing a lithium ion battery: winding the prepared positive plate, diaphragm and negative plate to obtain a bare cell without liquid injection; and placing the bare cell in an outer packaging aluminum foil, injecting the prepared electrolyte into the dried bare cell, and performing vacuum packaging, standing, formation, shaping, sorting and other procedures to obtain the required lithium ion battery, wherein the discharge voltage interval is set to be 3.0-4.5V.
Examples 2 to 10 and comparative examples 1 to 6
Examples 2 to 10 and comparative examples 1 to 6 were the same as example 1 except that the additive and electrolyte components were different in ratio. Specifically, the results are shown in Table 1.
TABLE 1
Test conditions
The lithium ion batteries prepared in examples 1 to 10 and comparative examples 1 to 6 were subjected to high temperature cycle and high temperature storage performance tests, respectively, as follows:
(1) High temperature cycle test: the battery is placed under the environment of 45 ℃, the formed battery is charged to 4.5V by using a constant current and a constant voltage of 1C, the cut-off current is 0.02C, and then the battery is discharged to 3.0V by using the constant current of 1C. After the charge/discharge cycle as such, the retention rate of the capacity after the cycle at 600 weeks was calculated to evaluate the cycle performance thereof.
The capacity retention rate after 600 cycles at 45℃was calculated as follows:
600 th cycle capacity retention (%) = (600 th cycle discharge capacity/first cycle discharge capacity) ×100%
(2) High temperature storage test: the formed battery is charged to 4.5V at 25 ℃ with a constant current and a constant voltage of 1C, the cut-off current is 0.02C, the constant current of 1C is then used for discharging to 3.0V, the initial discharge capacity of the battery is measured, the constant current and the constant voltage of 1C are then used for charging to 4.5V, the cut-off current is 0.02C, the initial volume of the battery is measured, the battery is stored at 60 ℃ for 14 days, the thickness of the battery after 60 ℃ is measured, the constant current of 1C is then used for discharging to 3.0V, the holding capacity of the battery is measured, the constant current and the constant voltage of 1C are then used for charging to 3.0V, the battery is cut off to 0.02C, the constant current of 1C is then used for discharging to 3.0V, and the recovery capacity is measured.
The calculation formulas of the capacity retention rate, the capacity recovery rate and the volume expansion are as follows:
battery capacity retention (%) =retention capacity/initial capacity ×100%
Battery capacity recovery rate (%) =recovery capacity/initial capacity ×100%
Cell volume expansion (%) = (volume after 14 days-initial volume)/initial volume 100%.
FIG. 1 is a graph showing the results of the test of capacity retention rate of the batteries of examples 1-2 and comparative examples 1-2 at a high temperature of 45℃for 600 weeks, and it can be seen from FIG. 1 that the capacity of examples 1 and 2 shows a tendency of gradual decay in the cycle because the double bonds of formula (1) break at the initial stage of the electrochemical reaction process, a dense solid electrolyte interface film can be formed at the positive and negative electrodes, and at the same time, formula (2) also participates in the film formation in an open loop, the ion dense stability of the interface film is enhanced, and the overall performance of the battery can be maintained stable for a long period of life; while comparative example 1 and comparative example 2 did not have the structures of the formulas (1) and (2), resulting in that the capacity exhibited a tendency of water jump at the time of circulation, and the capacity retention rates of examples 1 and 2 were 90% or more at the time of circulation to 600 weeks, whereas the capacity retention rates of comparative examples 1 and 2 were only kept under 83%, since the lithium battery capacity was considered to be attenuated to 80% or less in industry and had no value of reuse, it was reasonably presumed that examples 1 and 2 could continue to circulate for a plurality of weeks after 600 weeks, whereas comparative example 1 directly reached the life requirement of the lithium battery, and comparative example 2 also reached the life requirement in the next several weeks.
FIG. 2 is a graph showing the results of testing the capacity retention and recovery of the batteries of examples 1-2 and comparative examples 1-2 when stored at 60℃for 14 days; as can be seen from fig. 2, in examples 1 and 2, after the lithium battery is stored for 14 days, the capacity retention rate is more than 90% and the capacity recovery rate is more than 91%, so that the lithium battery can be stored for a period of time, because the-Si-O-bond can complex the metal ions dissolved out from the positive electrode under a high temperature environment, the catalytic reaction of the metal ions on the electrolyte is further reduced, the Si atoms are extremely easy to adsorb fluorine ions, and the decomposition of lithium salt is inhibited; the B atoms can coordinate with oxygen atoms in the positive electrode material, so that the crystal structure of the positive electrode material in a high-temperature environment is stabilized, and the stability of the positive electrode in the charge and discharge processes is protected; and the capacity retention rate and recovery rate of comparative examples 1 and 2 are below 68%, and the lithium battery already reaches the rejection standard.
FIG. 3 is a graph showing the results of the test of the volume increase rate of the batteries of examples 1-2 and comparative examples 1-2 stored at a high temperature of 60 ℃ for 14 days, and it can be seen from FIG. 3 that the volume expansion degree of examples 1 and 2 is smaller, but only 4.4% and 3.5%, because the surface of the lithium battery pole piece is film-formed stably after the structures of the formula (1) and the formula (2) are added, the structure of the positive electrode crystal is stable, gas is not easily generated, the permeability of lithium ions is strong, lithium dendrite is not easily generated by lithium precipitation on the surface of the negative electrode, and the pole piece is not thickened; while the absence of a stable environment inside the lithium batteries of comparative examples 1 and 2 resulted in expansion of the batteries to 15.2% and 6.8%, which is significantly larger than the volume size of the examples.
The test results of each example and comparative example are summarized in table 2.
TABLE 2
As can be seen from the data in Table 2, the present invention uses the nonaqueous electrolyte containing the combination of the cyclic alkenyl siloxane and the cyclic borane compound, and tests the high-voltage lithium ion battery prepared by the above examples to have high-temperature cycle and high-temperature storage performance, wherein the capacity retention rate is up to 91% or more after 600 cycles at 45 ℃ and 14 days of high-temperature storage at 60 ℃, the capacity retention rate is up to 90% or more, the capacity recovery rate is up to 91% or more, and the volume expansion rate is as low as 4.8% or less. This shows that the lithium ion battery prepared by the electrolyte has the advantages of high long-cycle retention rate, high storage capacity retention rate and high recovery rate.
Further, when the cyclic alkenyl siloxane and the cyclic borane compound are used in combination with lithium difluorophosphate, vinyl sulfate, fluoroethylene carbonate, 1, 3-propane sultone, ethylene glycol dipropylene nitrile ether, 1,3, 6-hexane tricarbonitrile, succinonitrile, adiponitrile, lithium difluorobisoxalato phosphate, 1,2, 3-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, the battery performance is better than that of the cyclic alkenyl siloxane or the cyclic borane compound additive alone, and the volume expansion rate of the battery after high-temperature storage is far smaller than that of the comparative example, so that the electrolyte provided by the invention has excellent high-temperature long-cycle stability and high-temperature storage stability and good safety performance when applied to a high-voltage lithium ion battery.
The acyclic alkenylsiloxane and cyclic borane compounds of comparative examples 1-4 exhibited capacity retention of less than 83% after 600 weeks of 45 ℃ cycle, capacity retention and recovery of less than 70% after 14 days of 60 ℃ high temperature storage, and the volume increase rate was far higher than that of the examples, indicating that the lithium battery at high voltage had excessively large impedance increase, poor lithium ion conductivity and dissolution of the positive electrode transition metal ions caused by high temperature, and continuous decomposition of the catalytic solvent was induced, thereby transiently consuming lithium ions, resulting in low capacity retention and recovery of the battery under high temperature conditions. And because solvent is decomposed continuously, on one hand, gas is generated, on the other hand, SEI film is further repaired continuously, SEI film is thickened continuously, pole piece is thickened, and the volume of the battery is increased on both sides.
As can be seen from comparison of examples with comparative examples 5 to 6, the cyclic alkenylsiloxane compound having the structure shown in formula (1) and the cyclic boroxine compound having the structure shown in formula (2) synergistically act, so that the battery has high capacity retention and recovery rates and a low volume expansion rate under high temperature conditions.
The applicant states that the present invention is described by way of the above examples as a lithium ion battery nonaqueous electrolyte and a lithium ion battery of the present invention, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (21)
1. A lithium ion battery nonaqueous electrolyte, characterized in that the lithium ion battery nonaqueous electrolyte comprises a lithium salt electrolyte, a nonaqueous solvent, and an additive comprising at least one cyclic alkenylsiloxane compound and at least one cyclic boroxine compound, the cyclic alkenylsiloxane compound being a cyclic alkenylsiloxane compound having a structure represented by formula (1) or 2,4,6, 8-octa (vinyl) -1,3,5,7,2,4,6,8-tetraoxatetrasiloxane, the cyclic boroxine compound being a cyclic boroxine compound having a structure represented by formula (2) or B03 or B06;
wherein R is 1 Selected from hydrogen, halogen, cyano, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C6-C30 aryl, amide, phosphate, sulfonyl, siloxy or borate, n is an integer from 3 to 10; r is R 2 Selected from hydrogen, halogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C6-C30 aryl, m is an integer from 3 to 10;
the content of the cyclic alkenylsiloxane compound having the structure represented by the formula (1) is 0.01 to 5% and the content of the cyclic boroxine compound having the structure represented by the formula (2) is 0.01 to 5% based on 100% of the total mass of the nonaqueous electrolyte solution for the lithium ion battery.
2. The nonaqueous electrolyte for lithium ion batteries according to claim 1, wherein when the group is a substituted group, the substituent is at least one selected from halogen, C1-C6 alkyl, and C1-C6 alkoxy.
3. The nonaqueous electrolyte for lithium ion batteries according to claim 1, wherein the cyclic alkenyl siloxane compound having a structure represented by formula (1) is any one of 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinyl cyclotetrasiloxane and tetravinyl tetraphenyl cyclotetrasiloxane.
4. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the cyclic borane compound having the formula (2) is any one of the following compounds:
5. the lithium ion battery nonaqueous electrolyte of claim 1, wherein the additive further comprises other additives comprising one or a combination of at least two of lithium difluorophosphate, vinyl sulfate, fluoroethylene carbonate, 1, 3-propane sultone, ethylene glycol dipropylene nitrile ether, 1,3, 6-hexanetrinitrile, succinonitrile, adiponitrile, lithium difluorobisoxalato phosphate, or 1,2, 3-tetrafluoroethyl-2, 3-tetrafluoropropyl ether.
6. The nonaqueous electrolyte for lithium ion batteries according to claim 5, wherein the content of the other additive is 0.01 to 25% based on 100% of the total mass of the nonaqueous electrolyte for lithium ion batteries.
7. The lithium ion battery nonaqueous electrolyte of claim 1, wherein the lithium salt electrolyte comprises any one or a combination of at least two of lithium hexafluorophosphate, lithium perchlorate, lithium triflate, lithium bis-fluorosulfonyl imide, or lithium bis-trifluoromethylsulfonyl imide.
8. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the content of the lithium salt electrolyte is 2 to 25% based on 100% of the total mass of the lithium ion battery nonaqueous electrolyte.
9. The nonaqueous electrolyte for lithium ion batteries according to claim 1, wherein the nonaqueous solvent is one or a combination of at least two of ethylene glycol diethyl ether, methyl propionate, methyl acetate, propyl propionate, methyl butyrate, ethyl butyrate, propyl acetate, butyl butyrate, acetonitrile, methyl propyl carbonate, ethyl propionate, γ -butyrolactone, sulfolane, dimethyl sulfoxide, tetrahydrofuran, propylene carbonate, ethyl acetate, diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, and ethylene carbonate.
10. The nonaqueous electrolyte for lithium ion batteries according to claim 1, wherein the content of the nonaqueous solvent is 40 to 92.98% based on 100% of the total mass of the nonaqueous electrolyte for lithium ion batteries.
11. A lithium ion battery, characterized in that the lithium ion battery comprises the lithium ion battery nonaqueous electrolyte according to any one of claims 1 to 10.
12. The lithium ion battery of claim 11, wherein the lithium ion battery comprises a battery housing, a battery cell, and the lithium ion battery nonaqueous electrolyte of any of claims 1-10, the battery cell and the lithium ion battery nonaqueous electrolyte being sealed within the battery housing.
13. The lithium ion battery of claim 12, wherein the cell comprises a positive electrode, a negative electrode, and a separator or solid electrolyte layer disposed between the positive electrode and the negative electrode.
14. The lithium ion battery of claim 13, wherein the positive electrode comprises an active material that can intercalate and deintercalate lithium.
15. The lithium ion battery according to claim 14, wherein the active material capable of inserting and extracting lithium is a lithium transition metal composite oxide.
16. The lithium ion battery of claim 13, wherein the negative electrode comprises a metal or alloy capable of intercalating and deintercalating lithium or forming an alloy with lithium or a metal oxide capable of intercalating/deintercalating lithium.
17. The lithium ion battery according to claim 16, wherein the active material capable of inserting and extracting lithium is LiNi x Co y Mn z L (1-x-y-z) O 2 、LiCo x' L (1-x') O2、LiNi x” L' y' Mn (2-x”-y') O 4 、Li z' MPO 4 、LiMn 2 O 4 At least one of (a) and (b); wherein L is at least one of Al, sr, mg, ti, ca, zr, zn, si, fe; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x+y+z is more than or equal to 0 and less than or equal to 1, x ' is more than or equal to 0 and less than or equal to 0.6, y ' is more than or equal to 0.01 and less than or equal to 0.2, and L ' is at least one of Co, al, sr, mg, ti, ca, zr, zn, si or Fe; and z' is more than or equal to 0.5 and less than or equal to 1, and M is at least one of Fe, mn or Co.
18. The lithium ion battery of claim 13, wherein the material of the negative electrode comprises crystalline carbon, lithium metal, siO 2 Graphite composite, siCGraphite composite, liMnO 2 、LiAl、Li 3 Sb、Li 3 Cd、LiZn、Li 3 Bi、Li 4 Si、Li 4.4 Pb、Li 4.4 Sn、LiC 6 、Li 3 FeN 2 、Li 2.6 CoN 0.4 、Li 2.6 CuN 0.4 Or Li (lithium) 4 Ti 5 O 12 At least one of them.
19. The lithium ion battery of claim 11, wherein the lithium ion battery has a charge cutoff voltage of not less than 3.6V.
20. The lithium ion battery of claim 11, wherein the operating voltage of the lithium ion battery is 3.6V to 5V.
21. The lithium ion battery of claim 20, wherein the operating voltage of the lithium ion battery is 4.35V to 4.8V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210149798.0A CN114512721B (en) | 2022-02-18 | 2022-02-18 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
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