CN116487707B - Lithium ion battery and electrolyte thereof - Google Patents
Lithium ion battery and electrolyte thereof Download PDFInfo
- Publication number
- CN116487707B CN116487707B CN202310724615.8A CN202310724615A CN116487707B CN 116487707 B CN116487707 B CN 116487707B CN 202310724615 A CN202310724615 A CN 202310724615A CN 116487707 B CN116487707 B CN 116487707B
- Authority
- CN
- China
- Prior art keywords
- additive
- lithium ion
- ion battery
- electrolyte
- battery electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 83
- 239000003792 electrolyte Substances 0.000 title claims abstract description 82
- 239000000654 additive Substances 0.000 claims abstract description 115
- 230000000996 additive effect Effects 0.000 claims abstract description 92
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 125000005587 carbonate group Chemical group 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 4
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 claims description 3
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 claims description 3
- 229910013067 LiBF 4 At Inorganic materials 0.000 claims description 3
- 229910010941 LiFSI Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Chemical group 0.000 claims description 3
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- GANXFQTZEVGPPI-UHFFFAOYSA-N fluorosulfonyloxyethene Chemical compound FS(=O)(=O)OC=C GANXFQTZEVGPPI-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 17
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 14
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 9
- 229940017219 methyl propionate Drugs 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 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 description 1
- VRZVZOAFGFXPKI-UHFFFAOYSA-N 4-fluoro-1,3,2-dioxathiolane 2,2-dioxide Chemical compound FC1COS(=O)(=O)O1 VRZVZOAFGFXPKI-UHFFFAOYSA-N 0.000 description 1
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910011624 LiNi0.7Co0.1Mn0.2O2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-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
- 230000002411 adverse Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 nickel-cobalt-aluminum Chemical compound 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-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
- H01M10/056—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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
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 discloses a lithium ion battery and an electrolyte thereof, wherein the electrolyte comprises lithium salt, an organic solvent and a combined additive, the combined additive comprises an additive A and an additive B, and the structural formula of the additive A is as follows
Description
Technical Field
The invention relates to a lithium ion battery and electrolyte thereof, in particular to lithium ion battery electrolyte and a lithium ion battery using the same, and belongs to the technical field of lithium ion batteries.
Background
The lithium ion battery is widely applied to the fields of mobile electronic equipment, electric automobiles, two-wheel electric automobiles, unmanned aerial vehicles and the like due to the characteristics of high energy density, long service life, no memory effect and the like. With the continued development of lithium ion battery powered products, there is a growing demand for energy density and lifetime of lithium ion batteries.
The electrolyte is taken as an important component of the lithium ion battery, and plays a vital role in the performance of the lithium ion battery. Because of the short duration of use in winter and the rapid decay of service life in summer, consumers want better low temperature/high temperature performance of lithium ion batteries, and meanwhile, the lithium ion batteries are also required to have longer service life. In order to provide the energy density of the lithium battery, the prior art is mostly prone to increase the charge cut-off voltage by using high nickel materials or positive electrode materials such as lithium cobaltate and negative electrode materials such as silicon carbon, and the operation is easy to cause side reactions of the positive electrode and the negative electrode and serious gas generation, so that the service life of the battery is accelerated and even jumps. The conventional method is to add a film forming additive into the electrolyte so as to inhibit side reaction, but the conventional film forming additive can cause increase of internal resistance of the battery, so that the long service life of the lithium ion battery can not be ensured, and meanwhile, the battery power performance, the system storage performance and the cycle performance can not be considered.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a lithium ion battery and electrolyte thereof, which can give consideration to the long service life and quick charge performance of the lithium ion battery and the low temperature/high temperature performance of the lithium ion battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a lithium ion battery electrolyte comprising a lithium salt, an organic solvent, and a combination additive comprising additive a and additive B; wherein the additive B is a sulfur-containing compound, and the structural formula of the additive A is shown as formula I:
，
formula I.
With reference to the first aspect, further, the additive B is any one or more of compounds shown in formula ii:
，
II, the step of setting the position of the base plate,
wherein R is 1 ~R 4 Independently selected from any one of hydrogen atom, halogen atom or alkyl group with 1-4 carbon atoms; x is oxygen or carbon atom; y is an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom, and a and b are independently selected from 0 or 1.
Preferably, the halogen atom is any one of F, cl, br, I.
Preferably, the additive B is any one or more of 1, 3-propane sultone, 3-fluoro-1, 3-propane sultone, 1, 3-propene sultone, vinyl sulfate, vinyl fluorosulfate, vinyl sulfite, methylene methane disulfonate and propylene sulfate.
Preferably, the mass fraction of the additive A in the electrolyte is 0.1% -4%; and/or the mass fraction of the additive B in the electrolyte is 0.1% -3%.
Preferably, the electrolyte further comprises other additives, the other additives being at least one of additives of carbonates, nitriles and boron-containing elements.
Preferably, the organic solvent is a carbonate solvent and/or a carboxylate.
Preferably, the organic solvent is carbonate solvent and carboxylate, wherein the mass fraction of carboxylate in the organic solvent is less than or equal to 30%.
Preferably, the lithium salt is LiPF 6 、LiFSI、LiTFSI、LiBF 4 At least one of them.
In a second aspect, the invention provides a lithium ion battery comprising a positive electrode, a negative electrode, a separation membrane and the electrolyte of the lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
the additive A can preferentially react at the positive and negative electrode interfaces of the lithium battery to form a stable interface film with low impedance, so that the power or multiplying power performance of the battery is improved; the additive A contains four fluorine atoms, so that the oxidation resistance of the anode interface film can be improved, and the oxidation resistance of the electrolyte can be improved; meanwhile, the two phosphorus-oxygen double bonds have stronger electron-withdrawing capability, can adsorb the transition metal of the positive electrode, stabilize the active layer of the positive electrode and can effectively inhibit the dissolution of metal ions in the active layer of the positive electrode; compared with the conventional low-impedance additive lithium difluorophosphate, the additive A has higher solubility in the electrolyte, can improve the ionic conductivity of the electrolyte and promote the formation of an interfacial film on the surface of an electrode.
The additive B is a sulfur-containing compound, can form a film on the interface of the positive electrode and the negative electrode preferentially, forms a compact interface film, and can inhibit the oxidation of the positive electrode to the electrolyte.
When the additive A and the additive B are used simultaneously, the additive A and the additive B have a synergistic effect, a composite interface film containing S-O-P-O-P-O-S groups of F element can be formed at the interface of the positive electrode and the negative electrode, the composite interface film is more compact and has lower impedance, meanwhile, the compound containing F, P, S element in the electrolyte can further improve the oxidation resistance of the interface of the positive electrode, and compared with the electrolyte adopting the independent additive, the electrolyte system has higher stability and lower interface impedance, and the ion conduction capacity is greatly improved.
The combined additives selected in the electrolyte provided by the invention have a synergistic effect, so that the high-temperature cycle life of the lithium ion battery can be obviously prolonged, and meanwhile, the low-temperature performance, the high-temperature storage capacity recovery rate and the gas production in the high-temperature storage process of the lithium ion battery can be improved.
The electrolyte provided by the invention also comprises any one or more of carbonic ester, nitrile and additives containing boron, so that the interface between the anode and the cathode can be further protected, and the comprehensive performance of the battery is improved.
The electrolyte solvent provided by the invention also contains carboxylic ester, and the carboxylic ester can widen the liquid range of the electrolyte, reduce the viscosity and further improve the low-temperature performance of the battery.
Detailed Description
The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
In the examples and comparative examples described below, reagents, materials and instruments used are commercially available unless otherwise specified.
The invention provides lithium ion battery electrolyte, which comprises lithium salt, an organic solvent and a combined additive, wherein the combined additive comprises an additive A and an additive B; the additive B is a sulfur-containing compound, and the structural formula of the additive A is shown as formula I:
，
formula I.
The mass fraction of the additive A in the electrolyte is 0.05% -5%, preferably 0.1% -4%. The additive A can form a stable interface film (SEI) with low impedance, and the compound contains 4F atoms, so that the oxidation resistance of the anode interface film can be improved, and meanwhile, the additive A has higher solubility in electrolyte (compared with a conventional low-impedance additive lithium difluorophosphate), and the cycle life and low-temperature performance of a lithium ion battery can be well improved.
The additive B is any one or more of compounds shown in a formula II:
，
II, the step of setting the position of the base plate,
wherein R is 1 ~R 4 Independently selected from any one of hydrogen atoms, halogen atoms or alkyl groups with 1-4 carbon atoms, wherein hydrogen on an alkyl carbon chain can be partially or completely substituted, and the halogen atoms are selected from one of F, cl, br, I; x is oxygen or carbon atom; y is an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom, wherein the halogen atom is any one of F, cl, br, I; a and b are independently selected from 0 or 1.
The additive B can be any one or more of sulfur-containing compounds, preferably 1, 3-Propane Sultone (PS), 3-fluoro-1, 3-propane sultone (FPS), 1, 3-propene sultone (PES), vinyl sulfate (DTD), fluoroethylene sulfate (FDTD), ethylene Sulfite (ES), methylene Methane Disulfonate (MMDS) and propylene sulfate (TS).
The mass fraction of the additive B in the electrolyte is 0.1% -4%, preferably 0.1% -3%. The sulfur-containing compound of the additive B can form a film on the interface of the anode and the cathode preferentially to form a compact interface film, can inhibit the oxidation of the anode to the electrolyte, and can well improve the cycle life and the high-temperature performance of the lithium ion battery.
The electrolyte can also contain other additives, wherein the mass fraction of the additives in the electrolyte is 0.1% -2%, and the additives are used for further protecting the anode-cathode interface and improving the comprehensive performance of the battery.
The other additives are at least one of carbonic ester, nitrile and boron-containing additives, and specifically, the carbonic ester additives are any one or more of fluoroethylene carbonate (FEC) and Vinylene Carbonate (VC); the nitrile additive is any one or more of Succinonitrile (SN), adiponitrile (ADN) and 1,3,6 Hexanetrinitrile (HTCN); the additive containing boron is one or more of lithium difluoroborate (LiDFOB), lithium dioxaborate (LiBOB) and triethyl borate.
The organic solvent in the electrolyte is carbonate solvent and/or carboxylate.
Preferably, the organic solvents in the electrolyte are carbonate solvents and carboxylic acid esters, comprising at least one cyclic carbonate, one linear carbonate and one carboxylic acid ester. The mass fraction of carboxylic acid esters in the organic solvent may be 30% or less, preferably 20% or less.
The organic solvent in the electrolyte is preferably any one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate.
The lithium salt in the electrolyte is LiPF 6 、LiFSI、LiTFSI、LiBF 4 At least one of them.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a separation film and lithium ion battery electrolyte. The positive electrode comprises any one or a combination of a plurality of nickel-cobalt-manganese ternary materials, nickel-cobalt-aluminum ternary materials, lithium iron phosphate, lithium iron manganese phosphate and lithium manganate; the negative electrode comprises any one or more of artificial graphite, natural graphite, soft carbon, hard carbon, silicon material and lithium metal.
Preferably, the silicon material of the present invention comprises a silicon carbon material and a silicon oxide material.
In the embodiment of the invention, the materials used for preparing the electrolyte are as follows:
organic solvent: ethylene Carbonate (EC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), methyl Propionate (MP);
lithium salt: liPF (LiPF) 6 ；
Additive A: the additive A is purchased from Shenzhen New Chun technology Co., ltd;
additive B:1, 3-Propane Sultone (PS), 3-fluoro-1, 3-propane sultone (FPS), vinyl sulfate (DTD), methylene Methane Disulfonate (MMDS), vinyl sulfite (ES);
other additives: vinylene Carbonate (VC), adiponitrile (ADN), lithium difluorooxalato borate (lidadiob);
the additives of the comparative examples were additionally added: lithium difluorophosphate (LiDFP) for comparison with additive A.
According to the preparation method, the electrolyte is prepared sequentially according to the following preparation methods of the embodiments 1-12:
firstly, slowly adding lithium salt into a mixed solution of EC, DMC and EMC in a glove box, cooling to room temperature in a container, then adding a combined additive, wherein the combined additive comprises an additive A, an additive B and other additives, and uniformly mixing to prepare the electrolyte. The mass ratio of EC, DMC and EMC in the electrolyte is EC: DMC: emc=3:3:4, the molar concentration of lithium salt in the electrolyte was 1mol/L.
Preparation of electrolyte according to example 13 of the present invention:
the preparation scheme of the electrolyte in the embodiment 13 of the invention is the same as the experimental steps of the embodiments 1 to 12, except for the proportion of the organic solvent. The mass ratio of the organic solvent EC, DMC, EMC to the MP in the electrolyte of this embodiment is EC: DMC: EMC: mp=3:3:3:1, mass fraction of MP in organic solvent is 10%.
Preparation of electrolyte according to example 14 of the present invention:
the preparation scheme of the electrolyte in the embodiment 14 of the invention is the same as the experimental steps of the embodiments 1 to 12, except for the proportion of the organic solvent. The mass ratio of the organic solvent EC, DMC, EMC to the MP in the electrolyte of this embodiment is EC: DMC: EMC: mp=3:3:2:2, mass fraction of MP in organic solvent is 20%.
The types and contents of the additives specifically used in examples 1 to 14 are shown in table 1, wherein the contents of the additives are weight percentages based on the total weight of the electrolyte.
Table 1: additive composition of the electrolytes of examples 1 to 14
Comparative examples 1 to 9 were prepared as follows:
firstly, slowly adding lithium salt into a mixed solution of EC, DMC and EMC in a glove box, and adding an additive after the temperature in a container is reduced to room temperature, wherein the specific composition and content of the additive are shown in Table 2, and the content of the additive is calculated as weight percentage based on the total weight of the electrolyte. After being uniformly mixed, the electrolyte is prepared; the mass ratio of EC, DMC and EMC in the electrolyte is EC: DMC: emc=3:3:4, the molar concentration of lithium salt in the electrolyte was 1mol/L.
Preparation of electrolyte in comparative example 10:
the preparation method of the electrolyte in comparative example 10 of the present invention is the same as the preparation steps of the electrolytes of comparative examples 1 to 9, except for the proportion of the organic solvent. The mass ratio of the organic solvent EC, DMC, EMC to the MP in the electrolyte of the comparative example is EC: DMC: EMC: mp=3:3:1:3, mass fraction of MP in organic solvent is 20%.
Table 2: the proportions of the additives of the electrolytes of comparative examples 1 to 10
Preparation of a lithium ion battery:
the electrolytes obtained in examples and comparative examples were respectively applied to lithium ion batteries prepared by the following steps:
(1) Preparation of positive plate
The positive electrode material nickel cobalt lithium manganate NCM712 (LiNi 0.7 Co 0.1 Mn 0.2 O 2 ) Mixing a binder (polyvinylidene fluoride) and a conductive agent (conductive carbon black) according to a mass ratio of 96:2:2, adding N-methyl pyrrolidone (NMP), and stirring to prepare anode slurry;
uniformly coating the positive electrode slurry on an aluminum foil, wherein the single-sided coating weight is 20mg/cm 2 ；
And (3) drying the coated aluminum foil at room temperature, transferring to a baking oven at 120 ℃ for drying for 1h, drying at 85 ℃ for cold pressing, trimming, cutting pieces and slitting, drying at 85 ℃ for 4h under vacuum condition, and welding the tab to prepare the positive plate of the lithium ion secondary battery meeting the requirements.
(2) Preparation of negative plate
Dissolving Artificial Graphite (AG), a thickener sodium carboxymethylcellulose (CMC) solution, a binder styrene-butadiene rubber emulsion (SBR) and a conductive agent (conductive carbon black) in deionized water according to a mass ratio of 96:1:1.5:1.5, and uniformly mixing to prepare negative electrode slurry;
uniformly coating the negative electrode slurry on a current collector copper foil, wherein the coating weight is 10mg/cm 2 And then drying at 85 ℃ for cold pressing, trimming, cutting pieces and splitting, drying at 110 ℃ for 4 hours under vacuum, and welding the tab to prepare the negative electrode piece of the lithium ion secondary battery meeting the requirements.
(3) Preparation of lithium ion batteries
And winding the positive plate, the negative plate and the isolating film (PE film+3um ceramic coating) into a bare cell, then filling the bare cell into an aluminum plastic film, baking at 90 ℃ to remove water, filling corresponding electrolyte, sealing, and performing the procedures of standing, hot and cold pressing, formation, exhaust, capacity division and the like to obtain the lithium ion battery.
The lithium ion battery obtained by the method is subjected to lithium ion battery performance test, which comprises the following performance tests:
(1) Lithium ion battery 45 ℃ high-temperature cycle performance test
The lithium ion battery is kept stand for 30 minutes at 45 ℃, then is charged to 4.3V at constant current with 0.5C multiplying power, and thenConstant voltage charging to 0.05C under 4.3V, standing for 5 min, and constant current discharging to 2.8V at 0.5C ratio, which is a charge-discharge cycle process, to obtain discharge capacity C which is the first discharge capacity of lithium ion battery 1H The method comprises the steps of carrying out a first treatment on the surface of the Then 1000 charge-discharge cycles are carried out, and the discharge capacity of the 1000 th cycle is recorded as C 1000 。
Capacity retention (%) =c after 1000 cycles of the lithium ion battery 1000H /C 1H 。
(2) Lithium ion battery low-temperature cycle performance test
Standing the lithium ion battery for 1h at-10 ℃, then charging to 4.3V at constant current with 0.5C multiplying power, then charging to 0.05C at constant voltage with 4.3V, standing for 5 min, then discharging to 2.8V with constant current with 1C multiplying power, wherein the discharge capacity is the first discharge capacity C of the lithium ion battery 1L The method comprises the steps of carrying out a first treatment on the surface of the Then 500 charge-discharge cycles are carried out, and the discharge capacity of 500 th cycle is recorded as C 500L 。
Capacity retention (%) =c after 500 cycles of the lithium ion battery 500L /C 1L 。
(3) 70 ℃ high-temperature storage test for lithium ion battery
Firstly, standing a lithium ion battery at 25 ℃ for 30 minutes; charging to 4.3V at a constant current of 0.5C, further charging to a current of 0.5C at a constant voltage of 4.3V; then the lithium ion battery was discharged at a constant current of 0.5C for 2.8V, at which time the discharge capacity was recorded as C 0s The method comprises the steps of carrying out a first treatment on the surface of the Charging to 4.3V with constant current of 0.5C, and further charging to 0.5C with constant voltage of 4.3V; finally, the volume of the battery is tested by a drainage method, wherein the volume is V before storage 0 . Then the lithium ion battery is stored for 30 days at 70 ℃, after the storage is finished, the lithium ion secondary battery is placed in an environment of 25 ℃, and the volume of the battery is tested by adopting a drainage method, wherein the volume is V after the storage 30 . Then discharging 2.8V to the lithium ion battery with a constant current of 0.5C; charging the lithium ion secondary battery to 4.3V with a constant current of 0.5C, and further charging the lithium ion secondary battery to 0.5C with a constant voltage of 4.3V; then discharging the lithium ion secondary battery to a constant current of 0.5C2.8V, the discharge capacity at this time was designated C 30s 。
Storage capacity recovery rate (%) =c after 30 days of lithium ion storage 30S /C 0S ；
Volume expansion rate (%) = (V) after 30 days of storage of the lithium ion battery 30 -V 0 )/V 0 。
The performance test data of the lithium ion batteries of the inventive examples and comparative examples are shown in table 3.
Table 3: test results of lithium ion battery
As can be seen from comparative examples 1 to 2, comparative example 4 and example 2 in table 3, the addition of additive a, additive B and a 45 ℃ cycle, -10 ℃ low temperature cycle, 70 ℃ storage capacity recovery and gas production performance of the combination of both in the lithium ion battery electrolyte are significantly improved compared with the blank electrolyte without any additive. Wherein, the additive A can form a stable interface film (SEI) with low impedance, and improves the high-temperature cycle and the low-temperature cycle more obviously; the sulfur-containing compound of the additive B can form a film on the interface of the anode and the cathode preferentially to form a compact interface film, can inhibit the oxidation of the anode to the electrolyte, and can improve the high-temperature circulation and the high-temperature storage obviously; the combination of the additive A and the additive B can better give consideration to the high-temperature cycle, the low temperature and the high-temperature storage performance of the lithium ion battery.
As can be seen from comparative examples 1-3, the combination property of the additive A added into the lithium ion battery is obviously better than that of LiDFP. Although the additive A and LiDFP can reduce the interfacial film of the anode and the cathode, the additive A has better film forming compactness and more obvious improvement on high-temperature circulation and storage; in addition, the solubility of the additive A in the electrolyte is far greater than that of LiDFP, the effective proportion of the additive A which actually plays a role is higher, and the improvement effect is more obvious.
As can be seen from examples 1 to 3 and comparative examples 4 to 6, as the mass fraction of the additive a in the electrolyte increases gradually from 0 to 6%, the cycle at 45 ℃, the recovery of the storage capacity at 70 ℃ and the gas production performance are all improved first and then the gradual effect is not remarkable, and it is presumed that when the content of the additive a increases to a certain content, the additive is rich and cannot be further improved; with the increase of the additive A, the cycle at-10 ℃ is gradually improved until the high content is slightly deteriorated, and the viscosity of the electrolyte is increased when the content of the additive is too high, which is presumed to be unfavorable for the transmission and diffusion of lithium ions at low temperature.
It is seen from examples 4 to 6 and comparative examples 7 to 8 that as the content of the sulfur-containing compound of the additive B increases, the high temperature cycle is not significantly improved to gradually act, while the low temperature and high temperature storage gas production is significantly improved to finally deteriorate, and it is presumed that when the content of the sulfur-containing compound such as DTD is too high or excessive, chemical decomposition occurs easily at high temperature, and by-products generated by decomposition adversely deteriorate the performance of the battery.
From examples 2, 5 and 7-12, it can be seen that the different types and content of the additive A and the additive B can be matched, so that the low-temperature cycle at-10 ℃, the 45 ℃ cycle, the storage capacity recovery at 70 ℃ and the gas production of the lithium ion battery can be comprehensively regulated and improved. It can be seen from examples 10 to 12 and comparative example 9 that the overall performance of the lithium ion battery can be further controlled by adding other additives based on the additive a and the additive B, but when the content of other additives such as VC is too high, a significant deterioration of part of the performance of the lithium ion battery occurs.
From examples 7, 13-14 and comparative example 10, it can be seen that the low-temperature cycle performance of the lithium ion battery can be further improved on the basis of not significantly deteriorating other performances by adding a suitable amount of carboxylic ester, the liquid path of the electrolyte can be widened by adding the carboxylic ester, and the carboxylic ester has higher conductivity and lower viscosity at low temperature; however, when the content of the carboxylic acid ester is too high, it is not resistant to oxidation-reduction and has a low boiling point, which deteriorates the high temperature performance of the lithium ion battery.
In summary, the combined additive in the electrolyte provided by the invention uses the additive A and the additive B in combination, so that the high-temperature cycle life of the lithium ion battery can be obviously prolonged, and meanwhile, the low-temperature performance of the lithium ion battery, the recovery rate of the high-temperature storage capacity and the gas production in the high-temperature storage process can be improved. And on the basis of the combination of the additive A and the additive B, other additives and carboxylic esters are added, so that the comprehensive performance of the lithium ion battery can be further regulated.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (9)
1. The lithium ion battery electrolyte is characterized by comprising lithium salt, an organic solvent and a combined additive, wherein the combined additive comprises an additive A and an additive B; the additive B is a sulfur-containing compound, and the structural formula of the additive A is shown as formula I:
，
a method for preparing the compound of formula I,
the additive B is any one or a combination of a plurality of compounds shown in a formula II:
，
II, the step of setting the position of the base plate,
wherein R is 1 ~R 4 Independently selected from any one of hydrogen atom, halogen atom or alkyl group with 1-4 carbon atoms; x is oxygen or carbon atom; y is an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom, and a and b are independently selected from 0 or 1.
2. The lithium ion battery electrolyte according to claim 1, wherein the halogen atom is any one of F, cl, br, I.
3. The lithium ion battery electrolyte according to claim 1, wherein the additive B is any one or more of 1, 3-propane sultone, 3-fluoro-1, 3-propane sultone, 1, 3-propene sultone, vinyl sulfate, vinyl fluorosulfate, vinyl sulfite, methylene methane disulfonate, and propylene sulfate.
4. The lithium ion battery electrolyte according to claim 1, wherein the mass fraction of the additive A in the electrolyte is 0.1% -4%; and/or the mass fraction of the additive B in the electrolyte is 0.1% -3%.
5. The lithium ion battery electrolyte of claim 1, wherein the electrolyte further comprises other additives, the other additives being at least one of carbonates, nitriles, and boron-containing additives.
6. The lithium ion battery electrolyte according to claim 1, wherein the organic solvent is a carbonate solvent and/or a carboxylate.
7. The lithium ion battery electrolyte according to claim 1, wherein the organic solvent is a carbonate solvent and a carboxylic ester, and wherein the mass fraction of the carboxylic ester in the organic solvent is less than or equal to 30%.
8. The lithium ion battery electrolyte of claim 1 wherein the lithium salt is LiPF 6 、LiFSI、LiTFSI、LiBF 4 At least one of them.
9. A lithium ion battery, characterized by comprising a positive electrode, a negative electrode, a separation film and the lithium ion battery electrolyte as claimed in any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310724615.8A CN116487707B (en) | 2023-06-19 | 2023-06-19 | Lithium ion battery and electrolyte thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310724615.8A CN116487707B (en) | 2023-06-19 | 2023-06-19 | Lithium ion battery and electrolyte thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116487707A CN116487707A (en) | 2023-07-25 |
| CN116487707B true CN116487707B (en) | 2023-09-22 |
Family
ID=87223533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310724615.8A Active CN116487707B (en) | 2023-06-19 | 2023-06-19 | Lithium ion battery and electrolyte thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116487707B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120127224A (en) * | 2024-12-13 | 2025-06-10 | 宁德时代新能源科技股份有限公司 | Battery cell, electrolyte, battery device and electricity utilization device |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008287965A (en) * | 2007-05-16 | 2008-11-27 | Bridgestone Corp | Non-aqueous electrolyte secondary battery |
| JP2009016134A (en) * | 2007-07-03 | 2009-01-22 | Bridgestone Corp | Gel electrolyte for polymer battery and polymer battery equipped with it |
| CN101507041A (en) * | 2006-08-22 | 2009-08-12 | 三菱化学株式会社 | Lithium difluorophosphate, electrolyte containing lithium difluorophosphate, method for producing nonaqueous electrolyte, and nonaqueous electrolyte secondary battery using same |
| CN109659614A (en) * | 2018-12-19 | 2019-04-19 | 珠海光宇电池有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery with high energy density using the electrolyte |
| JP2019169304A (en) * | 2018-03-22 | 2019-10-03 | 富山薬品工業株式会社 | Nonaqueous electrolyte solution for power storage device |
| CN114318368A (en) * | 2021-12-22 | 2022-04-12 | 广西汇元锰业有限责任公司 | Special electrolytic manganese dioxide for lithium manganate battery and preparation method and application thereof |
| KR20220158476A (en) * | 2021-05-24 | 2022-12-01 | 주식회사 켐얼라이언스 | New compound and electrolyte for secondary battery using the same |
-
2023
- 2023-06-19 CN CN202310724615.8A patent/CN116487707B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101507041A (en) * | 2006-08-22 | 2009-08-12 | 三菱化学株式会社 | Lithium difluorophosphate, electrolyte containing lithium difluorophosphate, method for producing nonaqueous electrolyte, and nonaqueous electrolyte secondary battery using same |
| JP2008287965A (en) * | 2007-05-16 | 2008-11-27 | Bridgestone Corp | Non-aqueous electrolyte secondary battery |
| JP2009016134A (en) * | 2007-07-03 | 2009-01-22 | Bridgestone Corp | Gel electrolyte for polymer battery and polymer battery equipped with it |
| JP2019169304A (en) * | 2018-03-22 | 2019-10-03 | 富山薬品工業株式会社 | Nonaqueous electrolyte solution for power storage device |
| CN109659614A (en) * | 2018-12-19 | 2019-04-19 | 珠海光宇电池有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery with high energy density using the electrolyte |
| KR20220158476A (en) * | 2021-05-24 | 2022-12-01 | 주식회사 켐얼라이언스 | New compound and electrolyte for secondary battery using the same |
| CN114318368A (en) * | 2021-12-22 | 2022-04-12 | 广西汇元锰业有限责任公司 | Special electrolytic manganese dioxide for lithium manganate battery and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116487707A (en) | 2023-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110931865A (en) | Novel additive-containing electrolyte for lithium ion battery and lithium ion battery | |
| CN110970662B (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN111106383A (en) | Electrolyte and lithium ion battery | |
| CN112448033A (en) | High-voltage lithium ion battery electrolyte and long-cycle-life high-voltage lithium ion battery | |
| CN114552010A (en) | Additive for lithium metal battery, electrolyte and lithium metal battery | |
| CN110416611B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
| CN116344937A (en) | Lithium ion battery and electrolyte thereof | |
| CN117691190A (en) | Electrolyte for lithium-rich manganese-based positive electrode high-voltage lithium ion battery and lithium ion battery | |
| CN111952667A (en) | Electrolyte additive, electrolyte containing additive and lithium ion battery | |
| CN116487707B (en) | Lithium ion battery and electrolyte thereof | |
| CN113113668B (en) | Electrolyte additive, non-aqueous electrolyte containing electrolyte additive and lithium ion battery | |
| CN110416609B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery comprising same | |
| CN118173892A (en) | Electrolyte and application thereof | |
| CN115763981B (en) | Electrolyte for lithium ion battery and application | |
| CN117790906A (en) | Additive for lithium ion battery electrolyte and lithium iron manganese phosphate battery electrolyte | |
| CN117766856A (en) | Nonaqueous electrolyte and lithium ion battery | |
| CN114583271B (en) | Electrolyte additive, electrolyte and lithium secondary battery | |
| CN114552015B (en) | Electrolyte additive, lithium ion battery electrolyte and lithium ion battery | |
| CN119108648A (en) | A lithium-manganese-rich lithium-ion battery | |
| CN110970663A (en) | Non-aqueous electrolytes and lithium-ion batteries | |
| CN110247116B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
| CN111146497B (en) | Additive for battery electrolyte, lithium ion battery electrolyte and lithium ion battery | |
| CN113594546A (en) | Electrolyte and application thereof | |
| CN112186246A (en) | Lithium salt electrolyte additive, electrolyte containing additive and lithium ion battery | |
| CN117497859B (en) | Lithium ion battery and electrolyte thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |