CN113801074A - Electrolyte additive, preparation method thereof, electrolyte and secondary battery - Google Patents
Electrolyte additive, preparation method thereof, electrolyte and secondary battery Download PDFInfo
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- CN113801074A CN113801074A CN202110881363.0A CN202110881363A CN113801074A CN 113801074 A CN113801074 A CN 113801074A CN 202110881363 A CN202110881363 A CN 202110881363A CN 113801074 A CN113801074 A CN 113801074A
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- Prior art keywords
- electrolyte
- additive
- electrolyte additive
- compound
- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 96
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 28
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 125000005843 halogen group Chemical group 0.000 claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 23
- 229910003002 lithium salt Inorganic materials 0.000 claims description 20
- 159000000002 lithium salts Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 15
- 229940126062 Compound A Drugs 0.000 claims description 13
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012454 non-polar solvent Substances 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 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
- 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 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 3
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-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
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 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
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 43
- 229910001416 lithium ion Inorganic materials 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 19
- 239000008151 electrolyte solution Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- OTNHJXWDXZJYKC-UHFFFAOYSA-N 4,7-dimethyl-5,6-dioxido-[1,2,5]oxadiazolo[3,4-d]pyridazine-5,6-diium Chemical compound CC1=[N+]([O-])[N+]([O-])=C(C)C2=NON=C12 OTNHJXWDXZJYKC-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007773 negative electrode material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000002210 silicon-based material Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- KLLQVNFCMHPYGL-UHFFFAOYSA-N 5h-oxathiole 2,2-dioxide Chemical compound O=S1(=O)OCC=C1 KLLQVNFCMHPYGL-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- MANBOMDQSILBJG-UHFFFAOYSA-N 2,3,4,5,6-pentafluoro-n-hydroxybenzamide Chemical compound ONC(=O)C1=C(F)C(F)=C(F)C(F)=C1F MANBOMDQSILBJG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 208000012266 Needlestick injury Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004809 thin layer chromatography 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
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
- C07D273/01—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having one nitrogen atom
-
- 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
- H01M10/0567—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
- H01M10/058—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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (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 belongs to the technical field of batteries, and particularly relates to an electrolyte additive, a preparation method thereof, an electrolyte and a secondary battery. The structural general formula of the electrolyte additive is shown as the following formula I:
formula I; wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkoxy and halogen, and R1、R2、R3、R4、R5At least one of which is a halogen atom or is substituted by a halogen atom. The electrolyte additive can form a compact SEI film on the surface of a negative electrode and a CEI film on the surface of a positive electrode, and the additive is not easy to form HF at high temperature and high pressure, has good stability, and effectively improves the stability of a positive electrode interface and a negative electrode interface, thereby improving the cycle life and the safety performance of a battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to an electrolyte additive, a preparation method thereof, an electrolyte and a secondary battery.
Background
The lithium ion battery has the advantages of high specific energy, long cycle life, no memory effect and the like, and is widely applied to the fields of mobile phones, computers, cameras, electric vehicles and the like. With the continuous development of scientific technology, various application fields put higher demands on the performance of the lithium ion battery, wherein the most urgent is to improve the energy density of the lithium ion battery on the premise of ensuring safety. At present, the industry is pursuing lithium batteries with high energy density and long cycle life. Therefore, the anode of the lithium ion battery generally adopts a high-nickel ternary material, and the cathode adopts a silicon-carbon material. Wherein, the high nickel material has strong oxidizing property to the electrolyte after the lithium removal, which causes the decomposition of the electrolyte, the gas generation of the battery, the dissolution of metal elements and the capacity attenuation. And the silicon-based material has huge volume expansion and shrinkage in the process of lithium intercalation and deintercalation, so that the SEI film on the surface of the silicon-based material is very easy to crack, and then the repeated growth of the SEI film is caused, and finally, a series of problems of battery impedance increase, flatulence, capacity attenuation and the like are caused. Therefore, the adoption of the materials all puts high requirements on the electrolyte additive.
Currently, numerous studies indicate that the cycle performance improvement of the silicon negative electrode is large with fluoroethylene carbonate (FEC). In order to improve the cycle performance of the silicon negative electrode, a high content of FEC is often used as a film forming additive in the existing electrolyte formula to cope with the volume expansion of the silicon negative electrode. However, the FEC is very easy to remove HF at high temperature to accelerate the decomposition of the carbonate electrolyte, which finally causes the battery to be very easy to generate gas at high temperature, and seriously affects the high-temperature cycle performance of the silicon negative electrode battery. And the reports of the additive aiming at a high nickel system are less, and the additive capable of forming films on the positive electrode and the negative electrode is less. Therefore, it is important to develop an electrolyte additive which can improve the interface stability of the silicon-carbon cathode and the interface stability of the nickel anode.
Disclosure of Invention
The invention aims to provide an electrolyte additive, a preparation method thereof, an electrolyte and a secondary battery, and aims to solve the problems that the existing electrolyte additive is easy to generate gas at high temperature and cannot be simultaneously applied to a high-nickel positive electrode system and a silicon negative electrode system to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides an electrolyte additive, wherein the structural general formula of the electrolyte additive is shown as formula I below:
wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkoxy and halogen, and R1、R2、R3、R4、R5At least one of which is a halogen atom or is substituted by a halogen atom.
The electrolyte additive provided by the first aspect of the invention can form a compact SEI film on the surface of a negative electrode and a CEI film on the surface of a positive electrode, and the additive is not easy to form HF under high temperature and high pressure, has good stability, and effectively improves the stability of a positive electrode interface and a negative electrode interface, thereby improving the cycle life and the safety performance of a battery.
Further, the electrolyte additive includes:
the electrolyte additive can form a compact SEI film on the surface of a negative electrode and a CEI film on the surface of a positive electrode under the action of active groups of the electrolyte additive, and the electrolyte additive is not easy to form HF at high temperature and high pressure, has good stability and can effectively improve the stability of a positive electrode interface and a negative electrode interface.
In a second aspect, the present invention provides a method for preparing an electrolyte additive, comprising the steps of:
dissolving the compound A and the compound B in a non-polar solvent, and then carrying out condensation reaction to obtain an electrolyte additive;
wherein the structural formula of the compound A is shown as the specification,
the structural formula of the compound B is shown as the specification,
wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkoxy and halogen, and R1、R2、R3、R4、R5At least one of which is a halogen atom or is substituted by a halogen atom.
According to the preparation method of the electrolyte additive provided by the second aspect of the invention, the raw material compound A and the compound B are dissolved in the solvent and then react to prepare the electrolyte additive, the preparation method is simple and is suitable for industrial large-scale production and application, and the prepared electrolyte additive can form a compact SEI film on the surface of a negative electrode and a compact CEI film on the surface of a positive electrode at the same time, has good high-temperature and high-pressure stability, is not easy to generate HF gas, so that the stability of a positive electrode interface and a negative electrode interface can be improved, and the cycle life and the safety performance of a battery can be improved.
Further, the conditions of the condensation reaction include: reacting for 10-30 minutes at the temperature of 20-40 ℃; under the condition, the raw material compound A and the compound B react to generate the electrolyte additive with the general structural formula I, and the preparation condition is temperature, simple to operate and high in efficiency.
Further, the molar ratio of compound a to compound B is 1: (2-2.5); the proportion can fully ensure the reaction between the compound A and the compound B to obtain the electrolyte additive with the structural general formula I.
Further, the nonpolar solvent is selected from at least one of dichloromethane, diisopropylamine, diethylamine, dipropylamine and dibutylamine, and the organic solvents have good solubility for the compound A and the compound B and provide a solvent environment for the reaction between the compounds.
Further, the electrolyte additive includes:
the electrolyte additive can form a compact SEI film on the surface of a negative electrode and a CEI film on the surface of a positive electrode under the action of active groups of the electrolyte additive, and the electrolyte additive is not easy to form HF at high temperature and high pressure, has good stability and can effectively improve the stability of a positive electrode interface and a negative electrode interface.
In a third aspect, the present invention provides an electrolyte comprising a lithium salt, an organic solvent and the electrolyte additive described above or the electrolyte additive prepared by the above method.
The electrolyte provided by the third aspect of the invention comprises lithium salt, an organic solvent and the electrolyte additive shown in the structural general formula I, and not only can a compact CEI film be formed on the surface of the anode, but also a compact SEI film can be formed on the surface of the cathode, and meanwhile, the electrolyte additive has good high-temperature and high-pressure stability, is not easy to generate HF gas, and simultaneously improves the stability of the anode and the cathode, thereby effectively prolonging the cycle life, and effectively improving the stability and safety performance of the battery.
Further, the electrolyte additive accounts for 0.1-10% by mass; the mass percentage content ensures that the electrolyte has the best film-forming property on the surfaces of the anode and the cathode, and simultaneously ensures the electrochemical comprehensive performance of the electrolyte.
Further, the mass percentage content of the lithium salt is 10-15%; the lithium salt with the content provides sufficient lithium ions for the electrolyte, so that the lithium ions can be inserted into and taken out of the positive electrode and the negative electrode, and the charge and discharge efficiency of the battery is ensured.
Furthermore, the electrolyte also comprises at least one auxiliary additive selected from vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, vinyl sulfate, 1-propylene-1, 3-sultone, ethylene carbonate, tris (trimethylsilane) phosphite, lithium bis-fluorosulfonylimide, lithium difluorophosphate and lithium difluorooxalato borate, and the auxiliary additives further improve the high-temperature stability of the electrolyte, improve the film forming effect of the electrolyte on the surface of an electrode and form an electrolyte film with excellent elasticity on the surface of the electrode, so that the interfacial reaction on the surface of the electrode is prevented, and the stability and the safety performance of the battery are improved.
Furthermore, the mass percentage of the same auxiliary additive in the electrolyte is 0.1-5%, and the auxiliary additive can further improve the high-temperature stability of the electrolyte and improve the film forming effect of the electrolyte on the surface of an electrode, so that the interface reaction on the surface of the electrode is prevented, and the stability and the safety performance of a battery are improved.
Further, the lithium salt is selected from LiPF6、LiBF4、LiPO2F2、LiTFSI、LiBOB、LiDFOB、LiCF3SO3、LiC(CF3SO2)3、LiB(C2O4)2、LiF(C2O4)2、LiN(CF3SO2)2、LiN(SO2F)2At least one of; the lithium salts are easy to dissociate lithium ions, and the lithium ions are inserted into and extracted from the positive electrode and the negative electrode, so that the cyclic charge and discharge of the battery are ensured.
Furthermore, the organic solvent is selected from at least one of ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, methyl formate, methyl acetate, methyl propionate, ethyl acetate, propyl propionate, sulfolane, gamma-butyrolactone and dimethyl sulfoxide, and the organic solvents have good compatibility with additives and lithium salts, and are beneficial to the transmission of lithium ions in the charging and discharging processes of the battery.
In a fourth aspect, the present invention provides a secondary battery comprising the above electrolyte.
The secondary battery provided by the fourth aspect of the invention comprises the electrolyte, on one hand, the elastic protective films can be formed on the surfaces of the positive electrode and the negative electrode simultaneously, so that the interface stability of the surfaces of the positive electrode and the negative electrode is improved, the gas generation of the battery is reduced, the volume expansion effect of the battery electrode in the charging and discharging process is effectively relieved, the cycle performance of the electrode material is improved, and the stability of the positive electrode and the negative electrode of the battery is improved; on the other hand, the high-temperature and high-pressure stability is good, the gas HF gas is not easy to generate, the safety performance of the battery is further improved, and the cycle life of the battery is further prolonged. Thus, the stability, safety performance, and cycle life of the secondary battery are significantly improved.
Further, the positive electrode of the secondary battery contains a high nickel positive electrode material; the anode includes a silicon-based anode material. The electrolyte additive can simultaneously participate in the formation of solid electrolyte interface film layers on the surfaces of the anode and the cathode, and simultaneously improves the stability of the anode and the cathode, so the electrolyte additive is particularly suitable for a battery system with the anode made of a high-nickel ternary material and the cathode made of a silicon-based material.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing an electrolyte additive according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the present invention, the term "and/or" describes the association relationship of the associated objects, and means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present invention, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present invention, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the mass in the description of the embodiments of the present invention may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the invention. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiments of the present invention provides an electrolyte additive, which has a general structural formula as shown in formula I below:
wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkoxy and halogen, and R1、R2、R3、R4、R5At least one of which is a halogen atom or is substituted by a halogen atom.
The electrolyte additive provided by the first aspect of the embodiment of the invention has a structural general formula shown in formula I, wherein R is1、R2、R3、R4、R5At least one of which is a halogen atom or is substituted by a halogen atom (i.e. when R is1～R5At least one of the groups contains halogen atom substituent when the electrolyte additive is alkyl or alkoxy), the electrolyte additive is halogenated derivative of triphenyl dioxazolinone, has higher reduction potential and lower oxidation potential, and has reactive groups. On one hand, the electrolyte additive is easy to lose electrons at the positive electrode, C-C bonds between halogenated benzene rings are broken, and a solid electrolyte interface layer (CEI film) is formed by oxidation, so that the interface stability of the positive electrolyte is improved; on the other hand, the electrolyte additive is easy to obtain electrons at the negative electrode, an N-O bond is broken, a reduction reaction is carried out, and a solvent is preferably participated in the formation of a solid electrolyte interface layer (SEI film) on the surface of the negative electrode, so that the compactness and the elasticity of the SEI film are improved. In addition, the additive has good thermal stability, HF gas is not easy to generate at high temperature and high pressure, and the safety performance of the electrolyte is improved. The electrolyte additive provided by the embodiment of the invention can form a compact SEI film on the surface of a negative electrode and a CEI film on the surface of a positive electrode, and the additive is not easy to form HF under high temperature and high pressure, has good stability, and effectively improves the positive electrodeThe stability of the cathode interface improves the cycle life and the safety performance of the battery.
In the electrolyte additive of the embodiment of the invention, a substituent R1、R2、R3、R4、R5At least one of hydrogen, alkyl, alkoxy and halogen, wherein the halogen can be fluorine, chlorine, bromine and the like. These substitutions can improve the film forming effect of the additive, optimize the redox potential of the electrolyte additive, improve the solubility of the electrolyte additive to lithium salts, and improve the compatibility of the additive with solvents.
The electrolyte additive provided by the embodiment of the invention can participate in the formation of the solid electrolyte interface film layers on the surfaces of the anode and the cathode at the same time, and can improve the stability of the anode and the cathode at the same time, so that the electrolyte additive can be simultaneously suitable for a battery system with the anode made of a high-nickel ternary material and the cathode made of a silicon-based material. The contact between the anode high nickel ternary material and the electrolyte can be reduced, the strong oxidizing property of the high nickel material to the electrolyte is reduced, and the gas generation of the battery is reduced; and the volume expansion and contraction stress of the silicon-based negative electrode material in the lithium desorption and intercalation process can be relieved, and the stability of the pole piece is improved. Thereby effectively improving the stability, energy density, safety and the like of the battery.
In some embodiments, the electrolyte additive comprises:
the electrolyte additive can form a compact SEI film on the surface of a negative electrode and a CEI film on the surface of a positive electrode under the action of active groups of the electrolyte additive, and the electrolyte additive is not easy to form HF at high temperature and high pressure, has good stability and can effectively improve the stability of a positive electrode interface and a negative electrode interface.
The electrolyte additive of the embodiment of the present invention can be prepared by the following embodiment method.
As shown in fig. 1, a second aspect of the embodiment of the present invention provides a method for preparing an electrolyte additive, including the steps of:
s10, dissolving the compound A and the compound B in a nonpolar solvent, and then carrying out condensation reaction to obtain an electrolyte additive;
wherein the structural formula of the compound A is shown as the specification,
the structural formula of the compound B is shown as the specification,
wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkoxy and halogen, and R1、R2、R3、R4、R5At least one of which is a halogen atom or is substituted by a halogen atom.
In the method for preparing the electrolyte additive according to the second aspect of the embodiments of the present invention, the raw material compound a and the compound B are dissolved in the solvent, and then the condensation reaction is performed to obtain the electrolyte additive. The preparation method is simple and suitable for industrial large-scale production and application, and the prepared electrolyte additive
And a compact SEI film can be formed on the surface of the negative electrode, a compact CEI film is formed on the surface of the positive electrode, the stability at high temperature and high pressure is good, HF gas is not easy to generate, the stability of a positive electrode interface and a negative electrode interface can be improved, and the cycle life and the safety performance of the battery are improved.
In some embodiments, the conditions of the condensation reaction include: reacting for 10-30 minutes at the temperature of 20-40 ℃; under the condition, the raw material compound A and the compound B can react to generate the electrolyte additive with the general structural formula I, and the preparation condition is temperature, simple to operate and high in efficiency.
In some embodiments, the molar ratio of compound a to compound B is 1: (2-2.5); the proportion can fully ensure the reaction between the compound A and the compound B to obtain the electrolyte additive with the structural general formula I.
In some embodiments, the non-polar solvent is at least one selected from dichloromethane, diisopropylamine, diethylamine, dipropylamine and dibutylamine, and the organic solvents have good solubility for both compound a and compound B, and provide a solvent environment for the reaction between the compounds.
In some embodiments, the electrolyte additive comprises:
the electrolyte additive can form a compact SEI film on the surface of a negative electrode and a CEI film on the surface of a positive electrode under the action of active groups of the electrolyte additive, and the electrolyte additive is not easy to form HF at high temperature and high pressure, has good stability and can effectively improve the stability of a positive electrode interface and a negative electrode interface.
In a third aspect of embodiments of the present invention, there is provided an electrolyte comprising a lithium salt, an organic solvent and an electrolyte additive thereon or prepared by the above method.
The electrolyte provided by the third aspect of the embodiment of the invention comprises a lithium salt, an organic solvent and the electrolyte additive shown in the structural general formula I, and as the additive can form a compact CEI film on the surface of the positive electrode and a compact SEI film on the surface of the negative electrode, the additive has good high-temperature and high-pressure stability, is not easy to generate HF gas, and improves the stability of the positive electrode and the negative electrode, the cycle life, the stability and the safety performance of the battery are effectively improved.
In some embodiments, the electrolyte additive is present in an amount of 0.1% to 10% by weight. The mass percentage of the additive in the electrolyte in the embodiment of the invention ensures that the electrolyte has the optimal film-forming property on the surfaces of the anode and the cathode, and simultaneously ensures the electrochemical comprehensive performance of the electrolyte. If the content of the electrolyte additive is too high, the protective film layer formed on the surface of the electrode is too thick, the impedance is too high, the ion migration transmission is not facilitated, and the electrochemical performance is reduced; if the content of the additive is too low, the film forming effect on the surfaces of the anode and the cathode is poor, the protection performance of the electrode is not obvious, and the cycling stability of the electrode cannot be effectively improved. In some embodiments, the electrolyte additive may be 0.1-1%, 1-2%, 2-3%, 3-5%, 5-7%, 7-9%, 9-10%, etc. by mass.
In some embodiments, the lithium salt is present in an amount of 10% to 15% by weight; the lithium salt with the content provides sufficient lithium ions for the electrolyte, so that the lithium ions can be inserted into and taken out of the positive electrode and the negative electrode, and the charge and discharge efficiency of the battery is ensured. In some embodiments, the lithium salt may be present in an amount of 10 to 11%, 11 to 12%, 12 to 13%, 13 to 14%, 14 to 15%, etc. by mass.
In some embodiments, the lithium salt is selected from LiPF6、LiBF4、LiPO2F2、LiTFSI、LiBOB、LiDFOB、LiCF3SO3、LiC(CF3SO2)3、LiB(C2O4)2、LiF(C2O4)2、LiN(CF3SO2)2、LiN(SO2F)2At least one of; the lithium salts are easy to dissociate lithium ions, and the lithium ions are inserted into and extracted from the positive electrode and the negative electrode, so that the cyclic charge and discharge of the battery are ensured.
In some embodiments, the electrolyte further comprises Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), vinyl sulfate (DTD), 1-propene-1, 3-sultone (PES), ethylene carbonate (VEC), tris (trimethylsilane) phosphite (TMSPi), lithium bis-fluorosulfonylimide (LiFSI), lithium difluorophosphate (LiPO)2F2) At least one auxiliary additive of lithium difluorooxalato borate (LiODFB); these auxiliary additives can further improve the high-temperature stability of the electrolyte, improve the film-forming effect of the electrolyte on the surface of the electrode, and form an electrolyte film with excellent elasticity on the surface of the electrode, thereby preventing the electrode from being damagedThe interface reaction of the surface improves the stability and the safety performance of the battery.
In some embodiments, the electrolyte contains 0.1-5% of the same auxiliary additive by weight. According to the embodiment of the invention, the high-temperature stability of the electrolyte can be further improved through the auxiliary additive, and the film forming effect of the electrolyte on the surface of the electrode is improved, so that the interface reaction on the surface of the electrode is prevented, and the stability and the safety performance of the battery are improved. If the amount of the additive is too large, the film formation resistance is too large and the solubility is lowered; if the amount of the additive is too small, the auxiliary effect is not significant.
In some embodiments, the organic solvent is at least one selected from the group consisting of ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, methyl formate, methyl acetate, methyl propionate, ethyl acetate, propyl propionate, sulfolane, γ -butyrolactone, and dimethyl sulfoxide, and the organic solvents have good compatibility with additives and lithium salts, and facilitate lithium ion transport during battery charging and discharging.
In some embodiments, the organic solvent in the electrolyte may be formulated by using a plurality of solvents selected from a mixed solvent of propylene carbonate, ethylene carbonate, diethyl carbonate and methylethyl carbonate. In some embodiments, a volume ratio of 25: 5: 60: 10 of a mixed organic solvent of Ethylene Carbonate (EC), Polycarbonate (PC), methylethyl carbonate (EMC) and diethyl carbonate (DEC), wherein EC is cyclic carbonate, having a high dielectric constant but a high viscosity, PC, EMC and DEC are linear esters, having a low viscosity but a low dielectric constant, and a balance between the viscosity of the solvent and the dielectric constant can be achieved by compounding, so that the ionic conductivity of the electrolyte is high and the viscosity is moderate.
In a fourth aspect of the present invention, a secondary battery is provided, wherein the secondary battery includes the above electrolyte.
The secondary battery provided by the fourth aspect of the embodiment of the invention comprises the electrolyte, on one hand, an elastic protective film can be formed on the surfaces of the positive electrode and the negative electrode simultaneously, so that the interface stability of the surfaces of the positive electrode and the negative electrode is improved, the gas generation of the battery is reduced, the volume expansion effect of the battery electrode in the charging and discharging process is effectively relieved, and the cycle performance of the electrode material is improved, thereby improving the stability of the positive electrode and the negative electrode of the battery; on the other hand, the high-temperature and high-pressure stability is good, the gas HF gas is not easy to generate, the safety performance of the battery is further improved, and the cycle life of the battery is further prolonged. Thus, the stability, safety performance, and cycle life of the secondary battery are significantly improved.
In the lithium ion battery of the embodiment of the invention, the anode, the cathode, the diaphragm and the like can be made of any materials meeting the requirements of practical application.
In some embodiments, the positive electrode of the secondary battery comprises a high nickel positive electrode material; the anode includes a silicon-based anode material. The electrolyte additive provided by the embodiment of the invention can simultaneously participate in the formation of the solid electrolyte interface film layers on the surfaces of the anode and the cathode, and simultaneously improves the stability of the anode and the cathode, so that the electrolyte additive is particularly suitable for a battery system with the anode made of a high-nickel ternary material and the cathode made of a silicon-based material. The contact between the anode high nickel ternary material and the electrolyte can be reduced, the strong oxidizing property of the high nickel material to the electrolyte is reduced, and the gas generation of the battery is reduced; and the volume expansion and contraction stress of the silicon-based negative electrode material in the lithium desorption and intercalation process can be relieved, and the stability of the pole piece is improved. Thereby effectively improving the stability, energy density, safety and the like of the battery.
In some embodiments, the positive electrode material may be a high nickel ternary material, lithium cobaltate, or the like ternary material. In some embodiments, the positive electrode material may be a high nickel ternary material such as Ni83, Ni50, Ni60, Ni70, Ni80, Ni88, Ni 90. In some embodiments, the positive electrode material may also be a lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, polyanionic positive electrode material, or the like.
In some embodiments, the negative electrode material may be a silicon-based negative electrode material, or a composite material of a silicon-based material and a graphite negative electrode material, a tin-based negative electrode material, or the like. In some embodiments, the negative electrode material may be carbon-coated silicon or silica, or a silicon-carbon negative electrode material in which carbon and silicon or silica are both mixed directly.
In some embodiments, the diaphragm may be a ceramic diaphragm, a rubberized diaphragm, or the like.
In order to clearly understand the details of the above-mentioned implementation and operation of the present invention by those skilled in the art and to obviously embody the advanced performance of the electrolyte additive, the preparation method thereof, the electrolyte and the lithium ion battery according to the embodiment of the present invention, the above-mentioned technical solution is exemplified by a plurality of embodiments.
Example 1
An electrolyte additive, the preparation of which comprises the steps of:
1.02g of carbonyldiimidazole
Added to freshly distilled 100mL of methylene chloride and 2.27g of pentafluorobenzoylhydroxylamine
Stirring the solution at room temperature for 10-30 minutes until a higher conversion rate is reached (the conversion rate is judged by TLC (thin layer chromatography)) to obtain an electrolyte additive FPDO,
an electrolyte, the preparation of which comprises the steps of:
in a glove box with water content less than 1ppm and oxygen content less than 2ppm, 250g of EC, 50g of PC, 600g of EMC and 100g of DEC are made into a mixed organic solvent, and then a proper amount of fully dried LiPF is added6So that the concentration of lithium salt in the electrolyte is 1mol/L, and the basic electrolyte is obtained. 1% FPDO was added to the base electrolyte to obtain an electrolyte.
A lithium ion battery prepared by the steps of:
mixing a positive electrode material Ni83, carbon black, a conductive agent CNT and polyvinylidene fluoride PVDF in a proportion of 100: 0.7: 0.6: 1.5, then coating on an aluminum foil with the thickness of 12 mu m, and then drying at 85 ℃ to obtain the positive plate.
Mixing a negative silicon carbon material, carbon black, Styrene Butadiene Rubber (SBR) and carboxymethyl cellulose (CMC) by the weight ratio of 100: 0.9: 1.9: 1, coating the mixture on a copper foil with the thickness of 8 mu m, and drying the copper foil at 90 ℃ to obtain the negative plate.
And thirdly, taking the ceramic diaphragm as a diaphragm, and making the ceramic diaphragm, the positive plate and the negative plate into the dry cell of the lithium ion battery in a winding mode.
Fourthly, a formation aging grading process: the electrolyte in the embodiment 1 is injected into a dry cell core of the lithium ion battery, then the cell core is sealed, and the lithium ion battery is placed at 45 ℃ for 48 hours to enable the electrolyte to be fully soaked. The simulated cell was charged to 3.5V at 0.05C, then to 3.7V at 0.1C, then to 3.9V at 0.2C, and then aged at 45 ℃ for 48 h. After aging, the capacitor is fully charged at 0.33C and then discharged to 2.75V at 0.33C, which is the capacity grading. To obtain the lithium ion battery
Example 2
An electrolytic solution which differs from example 1 in that: to the base electrolyte was added 2% FPDO.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in example 2 was used.
Example 3
An electrolytic solution which differs from example 1 in that: 2% FPDO and 2% VC were added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in example 3 was used.
Example 4
An electrolytic solution which differs from example 1 in that: 2% FPDO and 2% FEC were added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in example 4 was used.
Example 5
An electrolytic solution which differs from example 1 in that: 2% FPDO and 2% DTD were added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in example 5 was used.
Example 6
An electrolytic solution which differs from example 1 in that: 2% FPDO and 2% PS were added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in example 6 was used.
Example 7
An electrolytic solution which differs from example 1 in that: 2% FPDO and 2% PES were added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in example 7 was used.
Example 8
An electrolytic solution which differs from example 1 in that: 2% FPDO and 2% LFO were added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in example 8 was used.
Example 9
An electrolytic solution which differs from example 1 in that: to the base electrolyte was added 10% FPDO.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in example 9 was used.
Example 10
An electrolytic solution which differs from example 1 in that: 0.1% FPDO was added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in example 10 was used.
Example 11
An electrolytic solution which differs from example 1 in that: to the base electrolyte was added 11% FPDO.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in example 11 was used.
Comparative example 1
An electrolytic solution which differs from example 1 in that: FPDO was not added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in comparative example 1 was used.
Comparative example 2
An electrolytic solution which differs from example 1 in that: 2% VC was added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in comparative example 2 was used.
Comparative example 3
An electrolytic solution which differs from example 1 in that: 2% FEC was added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in comparative example 3 was used.
Comparative example 4
An electrolytic solution which differs from example 1 in that: 2% DTD was added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in comparative example 4 was used.
Comparative example 5
An electrolytic solution which differs from example 1 in that: 2% PS was added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in comparative example 5 was used.
Comparative example 6
An electrolytic solution which differs from example 1 in that: 2% PES was added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in comparative example 6 was used.
Comparative example 7
An electrolytic solution which differs from example 1 in that: 2% LFO was added to the base electrolyte.
A lithium ion battery which differs from example 1 in that: the electrolyte prepared in comparative example 7 was used.
Further, to verify the advancement of the examples of the present invention, the following performance tests were performed on the lithium ion batteries prepared in the respective examples and comparative examples:
1. normal temperature cycle test
The lithium ion batteries prepared in each example and comparative example (5 batteries in each condition, the results were averaged) were charged to 4.2V with 0.5C CC-CV in an incubator at 25. + -. 2 ℃ with a constant voltage of 0.05C current cut off, left for 30min after charging, discharged to 2.75V with 1C again, left for 30min, and thus continuously cycled 300 times. The capacity retention (%) is a percentage obtained by dividing the discharge capacity after 600 cycles by the first discharge capacity.
2. High temperature cycle test
The test temperature was 45. + -. 2 ℃ as the normal temperature cycle test.
3. High temperature storage test
The batteries after the aging and capacity grading of the compositions of the examples and comparative examples were completed (5 batteries for each condition, the results were averaged) were charged to 4.2V with 0.5C CC-CV, the current was cut off from the constant voltage to 0.05C, and the charge capacity was recorded as C0. Storing at 55 + -2 deg.C for 7 days, discharging at 1C to 2.75V after the battery is placed at room temperature for 5 hours, and recording the discharge capacity as C1Calculating a capacity retention ratio (%) ═ C1/C0100%. Then the battery is charged to 4.2V by 0.5C CC-CV, the current of 0.05C is cut off and the battery is fully charged, and the charging capacity is marked as C2Then discharged to 2.75V at 1C, and the discharge capacity is marked as C3Calculating a capacity recovery ratio (%) ═ C3/C2100%. The battery expansion (%) was calculated as a percentage obtained by subtracting the thickness before storage from the thickness after storage and dividing the obtained difference in thickness by the thickness before storage of the battery.
4. Needle stick test
Refer to the description of the test method for the needle-punched part in GB/T31485-2015.
The results of the above tests are shown in table 1 below:
TABLE 1
From the test results, the lithium ion batteries prepared in the embodiments 1 to 11 of the present invention, due to the addition of the electrolyte containing the structural general formula I, all exhibit good normal temperature and high temperature cycle performance, and have good high temperature storage stability, small volume expansion rate, high retention rate and recovery rate, and high puncture resistance. In contrast, in comparative example 1, when no electrolyte additive was added to the electrolyte, the cycle capacity retention rate and the high-temperature storage performance were significantly reduced, and the puncture test was not passed. In comparative examples 2 to 7, only the conventional auxiliary additive is added, so that the cycle stability, the storage performance and the puncture test passing rate of the lithium ion battery are also remarkably reduced.
Further, it is understood from comparison between examples 1 to 10 and example 11 that when the content of the electrolyte additive is too high, the performance of the lithium ion battery is also affected, and the cycle stability and the high-temperature storage performance of the battery are lowered.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The electrolyte additive is characterized in that the structural general formula of the electrolyte additive is shown as the following formula I:
wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkoxy and halogen, and R1、R2、R3、R4、R5At least one of which is a halogen atom or is substituted by a halogen atom.
2. The electrolyte additive of claim 1 wherein the electrolyte additive comprises:
3. The preparation method of the electrolyte additive is characterized by comprising the following steps of:
dissolving the compound A and the compound B in a non-polar solvent, and then carrying out condensation reaction to obtain an electrolyte additive;
wherein the structural formula of the compound A is shown as the specification,
the structural formula of the compound B is shown as the specification,
wherein R is1、R2、R3、R4、R5At least one selected from hydrogen, alkyl, alkoxy and halogen, and R1、R2、R3、R4、R5At least one of which is a halogen atom or is substituted by a halogen atom.
4. The method of preparing the electrolyte additive of claim 3, wherein the conditions of the condensation reaction include: reacting for 10-30 minutes at the temperature of 20-40 ℃;
and/or the molar ratio of the compound A to the compound B is 1: (2-2.5);
and/or the nonpolar solvent is selected from at least one of dichloromethane, diisopropylamine, diethylamine, dipropylamine and dibutylamine.
5. The method of preparing the electrolyte additive according to claim 4, wherein the electrolyte additive comprises:
6. An electrolyte comprising a lithium salt, an organic solvent and an electrolyte additive as claimed in any one of claims 1 to 2 or prepared by a process as claimed in any one of claims 3 to 5.
7. The electrolyte of claim 6, wherein the electrolyte additive is present in an amount of 0.1% to 10% by weight;
and/or the mass percentage content of the lithium salt is 10-15%;
and/or the electrolyte also comprises at least one auxiliary additive of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, vinyl sulfate, 1-propylene-1, 3-sultone, ethylene carbonate, tris (trimethylsilane) phosphite, lithium bis-fluorosulfonylimide, lithium difluorophosphate and lithium difluorooxalato borate.
8. The electrolyte of claim 7, wherein the lithium salt is selected from LiPF6、LiBF4、LiPO2F2、LiTFSI、LiBOB、LiDFOB、LiCF3SO3、LiC(CF3SO2)3、LiB(C2O4)2、LiF(C2O4)2、LiN(CF3SO2)2、LiN(SO2F)2At least one of;
and/or, in the electrolyte, the mass percentage content of the same auxiliary additive is 0.1-5%;
and/or the organic solvent is selected from at least one of ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, methyl formate, methyl acetate, methyl propionate, ethyl acetate, propyl propionate, sulfolane, gamma-butyrolactone and dimethyl sulfoxide.
9. A secondary battery comprising the electrolyte according to any one of claims 6 to 8.
10. The secondary battery of claim 9, wherein the positive electrode of the secondary battery comprises a high nickel positive electrode material; the anode includes a silicon-based anode material.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040197667A1 (en) * | 2003-03-24 | 2004-10-07 | Samsung Sdi Co., Ltd. | Non-aqueous electrolyte and a lithium secondary battery comprising the same |
| DE102017103334A1 (en) * | 2017-02-17 | 2018-08-23 | Westfälische Wilhelms-Universität Münster | Electrolyte additive for lithium-ion batteries |
| CN110291676A (en) * | 2017-02-17 | 2019-09-27 | 明斯特威斯特法伦威廉大学 | Electrolyte additive for lithium-ion battery systems |
| CN110400968A (en) * | 2018-04-25 | 2019-11-01 | 比亚迪股份有限公司 | A kind of nonaqueous electrolytic solution, the power battery containing the nonaqueous electrolytic solution and the vehicle containing the power battery |
| CN110858664A (en) * | 2018-08-24 | 2020-03-03 | 比亚迪股份有限公司 | Electrolyte, battery containing electrolyte and electric vehicle |
| CN111848321A (en) * | 2020-06-12 | 2020-10-30 | 南方科技大学 | Chiral aminated sulfoxide and preparation method thereof |
| CN112514131A (en) * | 2018-06-20 | 2021-03-16 | 特斯拉公司 | Dioxazolone and nitrile sulfites as lithium ion battery electrolyte additives |
-
2021
- 2021-08-02 CN CN202110881363.0A patent/CN113801074A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040197667A1 (en) * | 2003-03-24 | 2004-10-07 | Samsung Sdi Co., Ltd. | Non-aqueous electrolyte and a lithium secondary battery comprising the same |
| DE102017103334A1 (en) * | 2017-02-17 | 2018-08-23 | Westfälische Wilhelms-Universität Münster | Electrolyte additive for lithium-ion batteries |
| CN110291676A (en) * | 2017-02-17 | 2019-09-27 | 明斯特威斯特法伦威廉大学 | Electrolyte additive for lithium-ion battery systems |
| CN110400968A (en) * | 2018-04-25 | 2019-11-01 | 比亚迪股份有限公司 | A kind of nonaqueous electrolytic solution, the power battery containing the nonaqueous electrolytic solution and the vehicle containing the power battery |
| CN112514131A (en) * | 2018-06-20 | 2021-03-16 | 特斯拉公司 | Dioxazolone and nitrile sulfites as lithium ion battery electrolyte additives |
| CN110858664A (en) * | 2018-08-24 | 2020-03-03 | 比亚迪股份有限公司 | Electrolyte, battery containing electrolyte and electric vehicle |
| CN111848321A (en) * | 2020-06-12 | 2020-10-30 | 南方科技大学 | Chiral aminated sulfoxide and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ACS: "2649232-52-8/RN", 《STN REGISTRY数据库》 * |
| TANG, JING-JING 等: "Interweaving Visible-Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones", 《ANGEWANDTE CHEMIE, INTERNATIONAL EDITION》 * |
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