WO2022262232A1 - Non-aqueous electrolyte and secondary battery - Google Patents
Non-aqueous electrolyte and secondary battery Download PDFInfo
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- WO2022262232A1 WO2022262232A1 PCT/CN2021/139145 CN2021139145W WO2022262232A1 WO 2022262232 A1 WO2022262232 A1 WO 2022262232A1 CN 2021139145 W CN2021139145 W CN 2021139145W WO 2022262232 A1 WO2022262232 A1 WO 2022262232A1
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- WIPO (PCT)
- Prior art keywords
- lithium
- compound
- structural formula
- electrolytic solution
- electrolyte
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 17
- -1 cyclic carbonate compound Chemical class 0.000 claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract 4
- 229940126062 Compound A Drugs 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000006259 organic additive Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 8
- KAEZJNCYNQVWRB-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] KAEZJNCYNQVWRB-UHFFFAOYSA-K 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 26
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000007747 plating Methods 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 30
- 238000001556 precipitation Methods 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 229910011322 LiNi0.6Mn0.2Co0.2O2 Inorganic materials 0.000 description 2
- 229910012424 LiSO 3 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 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
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 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
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000011701 zinc Substances 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
- H01M10/052—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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0034—Fluorinated 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
Definitions
- the present application relates to the field of energy storage devices, in particular to a non-aqueous electrolyte and a secondary battery thereof.
- Lithium-ion batteries are a common secondary battery.
- the positive electrode materials of commercial lithium-ion batteries mainly include lithium manganese oxide, lithium cobalt oxide, ternary materials, and lithium iron phosphate.
- the charging cut-off voltage generally does not exceed 4.2V.
- high-voltage (4.35V-5V) cathode materials are one of the more popular research directions. It achieves high energy density of batteries by increasing the charging depth of cathode active materials.
- the performance of the battery such as charge and discharge cycles decreases.
- the electrolyte as an important part of the lithium-ion battery, has a significant impact on the performance degradation of the battery charge and discharge cycle.
- the electrolyte determines the migration rate of lithium ions (Li + ) in the liquid phase, and also participates in the formation of the solid electrolyte interface (SEI) film, which plays a key role in the performance of the SEI film.
- SEI solid electrolyte interface
- High-temperature storage performance is poor, high-temperature cycle performance is poor, and normal temperature cycle performance is poor; at the same time, the viscosity of the electrolyte increases at low temperatures, the conductivity decreases, and the impedance of the SEI film increases, so the electrolyte may also cause low-temperature discharge of lithium-ion batteries. The performance is poor, and there is even a risk of low-temperature lithium precipitation.
- the purpose of this application is to provide a non-aqueous electrolyte and its secondary battery.
- This non-aqueous electrolyte can not only improve the high-temperature cycle performance, normal temperature cycle performance, rate performance, and low-temperature discharge performance of the secondary battery, but more importantly, it can Effectively avoid low-temperature lithium precipitation, so it can meet the requirements of high energy density and high voltage ternary material batteries.
- the first aspect of the present application provides a non-aqueous electrolyte, including lithium salt, non-aqueous organic solvent and additives
- the additives include cyclic sulfonimide compounds and fluorinated cyclic carbonates compound
- the structural formula of the cyclic sulfonimide compound is structural formula 1 or structural formula 2
- the structural formula of the fluorinated cyclic carbonate compound is structural formula 3, structural formula 4 or structural formula 5
- M + is Li + , Na + , K + , Cs + , and R 1 is H or an alkyl group.
- the additives in this application include cyclic sulfonimide compounds and fluorinated cyclic carbonate compounds.
- the fluorinated cyclic carbonate compounds can form a LiF-rich interfacial film on the negative electrode during the first charge and discharge stage. This layer of interfacial film can significantly increase the penetration and diffusion ability of lithium ions at the negative electrode interface, so it can effectively increase the lithium ion density. Low temperature and rate performance of ion batteries.
- the fluorinated cyclic carbonate compounds will be gradually consumed with the cycle of lithium-ion batteries, and more interfacial films containing LiF will be formed, but components such as LiF will be scattered in the later stage or after long cycles at low temperatures.
- adding cyclic sulfonylimide compounds can form an outer interface film containing a large amount of LiSO 3 , ROSO 2 Li, Li x N y O z , sulfur atoms and oxygen on the positive and negative electrodes during the first charge and discharge stage. Atoms all contain lone pairs of electrons and can attract Li + , thereby speeding up Li + shuttling in the solid electrolyte interface film.
- the interface film components formed by nitrogen atoms are tough, not easy to break, and have strong high temperature resistance, while the double bonds in the ring can Polymerization to form a "layered" structure of the negative electrode interface film can make LiF and other components evenly dispersed on the surface of the negative electrode, so that the transition metal ions dissolved from the positive electrode cannot enter the interior of the negative electrode and cause the battery to "suddenly dive".
- the combination of the two can effectively avoid the further consumption of a single fluorinated cyclic carbonate compound in the electrolyte and the reaction between the electrolyte and the negative electrode interface, thus greatly enhancing the high temperature and cycle performance of the lithium-ion battery.
- the combination of these additives can enhance the high-temperature cycle performance, normal-temperature cycle performance, low-temperature discharge performance and rate performance of the lithium-ion battery while inhibiting its lithium precipitation.
- M + is preferably Li + , K + , Cs +
- R 1 is preferably H or a C 1 -C 3 alkyl group.
- the mass percentage of cyclic sulfonimide compounds in the non-aqueous electrolyte is 0.1-0.5%, specifically but not limited to 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, cyclic sulfonyl
- the imine compound is selected from at least one of compound A to compound E,
- Compound C was synthesized similarly to Compound A, with the difference that LiOH was replaced by CsOH.
- Compound A, Compound C and Compound E can all be obtained by reacting Compound B as a raw material.
- the mass percentage of the fluorinated cyclic carbonate compound in the non-aqueous electrolyte is 0.5-10%, specifically but not limited to 0.5%, 0.7%, 0.9%, 1.0%, 1.2%, 1.5%, 2.0%, 2.3%, 2.5%, 3.0%, 3.5%, 3.8%, 4.3%, 5.0%, 5.7%, 6.0%, 7.0%, 8.0%, 8.5%, 9.0%, 9.3%, 9.6%, 10% .
- the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ), lithium difluorophosphate (LiPO 2 F 2 ), lithium bisoxalate borate (C 4 BLiO 8 ), lithium difluorooxalate borate (C 2 BF 2 LiO 4 ), di Lithium fluorodioxalate phosphate (LiDFBP), lithium tetrafluoroborate (LiBF 4 ), lithium tetrafluorooxalate phosphate (LiPF 4 C 2 O 4 ), lithium bistrifluoromethanesulfonimide (LiN(CF 3 SO 2 ) 2 ) and at least one of lithium bisfluorosulfonyl imide (LiFSI), the concentration of the lithium salt in the non-aqueous electrolyte is 0.5-2.5 mol/L.
- the lithium salt is LiPF 6 or a mixture of LiPF 6 and other lithium salts.
- the non-aqueous organic solvent is selected from ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC), ethyl acetate (Ea), butyl acetate (n-Ba), ⁇ -butyrolactone ( ⁇ -Bt), propyl propionate (n-Pp), ethyl propionate (EP) and ethyl butyrate (Eb) at least one of .
- EC ethylene carbonate
- DMC dimethyl carbonate
- DEC diethyl carbonate
- EMC ethyl methyl carbonate
- PC propylene carbonate
- Ea ethyl acetate
- n-Ba butyl acetate
- ⁇ -butyrolactone ⁇ -Bt
- propyl propionate n-Pp
- EP ethyl propionate
- Eb e
- the secondary battery of the present application includes a positive electrode, a negative electrode, an electrolyte and a separator for isolating the positive electrode and the negative electrode, and the electrolyte is the aforementioned non-aqueous electrolyte.
- the additives of the non-aqueous electrolyte of the secondary battery of the present application include cyclic sulfonimide compounds and fluorinated cyclic carbonate compounds, which can make the secondary battery have excellent high-temperature cycle performance, normal temperature cycle performance, and rate performance And low-temperature discharge performance, and can effectively avoid low-temperature lithium precipitation, so it can meet the requirements of high-energy density, high-voltage ternary material batteries.
- the positive active material is LiNixCoyMnzM (1- xyz ) O2 or LiNixCoyAlzN ( 1- xyz ) O2 , wherein M is Mg, Cu, Zn, Al, Any one of Sn, B, Ga, Cr, Sr, V and Ti, N is any one of Mn, Mg, Cu, Zn, Sn, B, Ga, Cr, Sr, V and Ti, 0.5 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1,0 ⁇ z ⁇ 1, x+y+z ⁇ 1, and the highest charging voltage is 4.35-4.5V.
- the active material of the negative electrode is at least one selected from artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material and silicon oxide.
- LiNi 0.6 Mn 0.2 Co 0.2 O 2 ternary material LiNi 0.6 Mn 0.2 Co 0.2 O 2 , binder PVDF and conductive agent SuperP are uniformly mixed at a mass ratio of 97.5:1.5:1 to make lithium ions with a certain viscosity
- the positive electrode slurry of the battery after coating the mixed slurry on both sides of the aluminum foil, drying and rolling to obtain the positive electrode sheet.
- lithium-ion battery the positive electrode, diaphragm and negative electrode are stacked into square batteries, packed in polymer, filled with the non-aqueous electrolyte of lithium-ion battery prepared above, and processed by chemical formation, volume separation, etc. After the process, a lithium-ion battery with a capacity of 2000mAh is made.
- the lithium-ion batteries made in Examples 1-8 and Comparative Examples 1-3 were respectively subjected to normal temperature cycle performance, high temperature cycle performance, low-temperature discharge test, high-rate discharge test and low-temperature lithium analysis test.
- the specific test conditions are as follows, and the performance test results As shown in table 2.
- Capacity retention discharge capacity of the last cycle/discharge capacity of the first cycle ⁇ 100%.
- Capacity retention discharge capacity of the last cycle/discharge capacity of the first cycle ⁇ 100%.
- Battery capacity retention rate (%) retention capacity/initial capacity ⁇ 100%.
- Battery capacity retention rate (%) retention capacity/initial capacity ⁇ 100%.
- the lithium-ion battery in an oven at a constant temperature of -10°C, charge it with a constant current of 0.5C to 4.5V, then charge it with a constant voltage until the current drops to 0.05C, and then discharge it with a constant current of 0.5C to 3.0V, so Cycle for 40 cycles, disassemble the battery, and observe the lithium-ion battery negative electrode surface lithium precipitation.
- the interface film components formed by nitrogen atoms are tough, not easy to break, and have strong high temperature resistance, while the double bonds in the ring can be polymerized to form "
- the layered structure of the negative electrode interface film can make LiF and other components evenly dispersed on the surface of the negative electrode, so that the transition metal ions dissolved from the positive electrode cannot enter the interior of the negative electrode and cause the battery to "suddenly dive".
- comparative example 2 contains a cyclic sulfonimide compound, the interfacial film formed by it can inhibit lithium precipitation and has high stability, and can improve the cycle performance to a certain extent, but the ability to conduct electrons is not good, so low temperature and discharge Performance is poor.
- the fluorinated cyclic carbonate compound in Comparative Example 3 can form a LiF-rich interfacial film on the negative electrode during the first charge and discharge stage.
- This layer of interfacial film can significantly increase the penetration and diffusion ability of lithium ions at the negative electrode interface, so it can Increase the low-temperature and rate performance of lithium-ion batteries, but after cycling to the later stage or long-term cycling under low temperature conditions, the problem of lithium precipitation cannot be solved.
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Abstract
A non-aqueous electrolyte and a secondary battery. The non-aqueous electrolyte comprises a lithium salt, a non-aqueous organic solvent, and an additive. The additive comprises a cyclic sulfonylimine compound and a fluorinated cyclic carbonate compound. The structural formula of the cyclic sulfonylimine compound is structural formula 1 or structural formula 2, and the structural formula of the fluorinated cyclic carbonate compound is structural formula 3, structural formula 4, or structural formula 5, wherein M+ is Li+, Na+, K+, or Cs+, and R1 is H or alkyl. In the present invention, the combination of the cyclic sulfonylimine compound and the fluorinated cyclic carbonate compound can effectively avoid further consumption of a single fluorinated cyclic carbonate compound in the electrolyte and the reaction between the electrolyte and an negative electrode interface, and thus, lithium plating can be suppressed while the high-temperature cycle performance, normal-temperature cycle performance, low-temperature discharge performance, and the rate capability of the lithium ion battery can be improved.
Description
本申请涉及储能器械领域，具体涉及一种非水电解液及其二次电池。The present application relates to the field of energy storage devices, in particular to a non-aqueous electrolyte and a secondary battery thereof.
二次电池具有比能量高、比功率大、循环寿命长、自放电小等显著优点，锂离子电池是一种常见的二次电池。商业用锂离子电池的正极材料主要有锰酸锂、钴酸锂、三元材料、磷酸亚铁锂几种，其充电截止电压一般不超过4.2V，随着科技的进步及市场的不断发展，提升锂离子电池的能量密度日益显得重要而迫切。Secondary batteries have significant advantages such as high specific energy, high specific power, long cycle life, and small self-discharge. Lithium-ion batteries are a common secondary battery. The positive electrode materials of commercial lithium-ion batteries mainly include lithium manganese oxide, lithium cobalt oxide, ternary materials, and lithium iron phosphate. The charging cut-off voltage generally does not exceed 4.2V. With the advancement of technology and the continuous development of the market, It is increasingly important and urgent to increase the energy density of lithium-ion batteries.
除了现有材料和电池的制作工艺改进之外，高电压(4.35V-5V)正极材料是对比热门的研究方向之一，它是通过提升正极活性材料的充电深度来实现电池的高能量密度。然而三元材料电池工作电压提高后，电池的充放电循环等性能却下降。其中，电解液作为锂离子电池的重要组成部分，对电池的充放电循环等性能下降有着重大的影响。电解液决定了锂离子(Li
+)在液相中的迁移速率，同时还参与固体电解质界面(SEI)膜形成，对SEI膜性能起着关键性的作用，故而电解液可能导致锂离子电池的高温储存性能较差、高温循环性能较差、常温循环性能较差；同时低温下电解液的黏度增大，电导率降低，SEI膜阻抗增大，故电解液还可能导致锂离子电池的低温放电性能较差，甚至产生低温析锂的风险。
In addition to the improvement of existing materials and battery manufacturing processes, high-voltage (4.35V-5V) cathode materials are one of the more popular research directions. It achieves high energy density of batteries by increasing the charging depth of cathode active materials. However, after the operating voltage of the ternary material battery is increased, the performance of the battery such as charge and discharge cycles decreases. Among them, the electrolyte, as an important part of the lithium-ion battery, has a significant impact on the performance degradation of the battery charge and discharge cycle. The electrolyte determines the migration rate of lithium ions (Li + ) in the liquid phase, and also participates in the formation of the solid electrolyte interface (SEI) film, which plays a key role in the performance of the SEI film. High-temperature storage performance is poor, high-temperature cycle performance is poor, and normal temperature cycle performance is poor; at the same time, the viscosity of the electrolyte increases at low temperatures, the conductivity decreases, and the impedance of the SEI film increases, so the electrolyte may also cause low-temperature discharge of lithium-ion batteries. The performance is poor, and there is even a risk of low-temperature lithium precipitation.
因此，亟需研发一种各方面性能优异的非水电解液以满足高能量密度三元材料电池的使用要求。Therefore, there is an urgent need to develop a nonaqueous electrolyte with excellent performance in all aspects to meet the requirements of high energy density ternary material batteries.
申请内容application content
本申请的目的在于提供一种非水电解液及其二次电池，此非水电解液不仅 可提高二次电池的高温循环性能、常温循环性能、倍率性能、低温放电性能，更重要的是能有效避免低温析锂，故可满足高能量密度、高电压的三元材料电池的使用要求。The purpose of this application is to provide a non-aqueous electrolyte and its secondary battery. This non-aqueous electrolyte can not only improve the high-temperature cycle performance, normal temperature cycle performance, rate performance, and low-temperature discharge performance of the secondary battery, but more importantly, it can Effectively avoid low-temperature lithium precipitation, so it can meet the requirements of high energy density and high voltage ternary material batteries.
为实现上述目的，本申请第一方面提供了一种非水电解液，包括锂盐、非水有机溶剂和添加剂，所述添加剂包括环状磺酰亚胺类化合物和氟代环状碳酸酯类化合物，所述环状磺酰亚胺类化合物的结构式为结构式1或结构式2，所述氟代环状碳酸酯类化合物的结构式为结构式3、结构式4或结构式5，In order to achieve the above object, the first aspect of the present application provides a non-aqueous electrolyte, including lithium salt, non-aqueous organic solvent and additives, the additives include cyclic sulfonimide compounds and fluorinated cyclic carbonates compound, the structural formula of the cyclic sulfonimide compound is structural formula 1 or structural formula 2, the structural formula of the fluorinated cyclic carbonate compound is structural formula 3, structural formula 4 or structural formula 5,
其中，M
+为Li
+、Na
+、K
+、Cs
+，R
1为H或烷基。
Wherein, M + is Li + , Na + , K + , Cs + , and R 1 is H or an alkyl group.
本申请的添加剂包括环状磺酰亚胺类化合物和氟代环状碳酸酯类化合物。其中，氟代环状碳酸酯类化合物可在首次充放电阶段于负极形成富含LiF的界面膜，该层界面膜能明显增加锂离子在负极界面的穿透与扩散能力，故而能有效增加锂离子电池的低温与倍率性能。但氟代环状碳酸酯类化合会随着锂离子电池的循环逐渐被消耗，并形成更多的含有LiF的界面膜，但循环到后期或在低温条件下长循环后LiF等组分会散乱无规则地堆积在负极表面，随着负极的膨胀该界面膜极易破裂引起电解液与负极的副反应，并使得从正极溶出的过渡金属离子穿过LiF层进入到负极内部阻塞锂离子进入负极的孔道，导致局部形成“死锂”，即析锂而致电池循环后期“突然跳水”。基于此，增加环状磺酰亚胺类化合物，其可在首次充放电阶段在正极和负极形成含大量LiSO
3、ROSO
2Li、 Li
xN
yO
z的外层界面膜，硫原子和氧原子由于皆含有孤对电子进而可吸引Li
+，从而加快Li
+在固体电解质界面膜中穿梭，氮原子形成的界面膜组分富有韧性，不易破裂、耐高温性能强，而环内双键能聚合形成“层状”结构的负极界面膜，可使得LiF等组分均匀分散在负极表面，进而使得正极溶出的过渡金属离子不能进入负极内部而引发电池“突然跳水”。总的来说，两者组合能有效的避免电解液中单一氟代环状碳酸酯类化合进一步消耗以及电解液与负极界面的反应，因而大大增强了锂离子电池的高温和循环性能，通过两种添加剂的结合，能于增强锂离子电池的高温循环性能、常温循环性能、低温放电性能和倍率性能的同时抑制其析锂。
The additives in this application include cyclic sulfonimide compounds and fluorinated cyclic carbonate compounds. Among them, the fluorinated cyclic carbonate compounds can form a LiF-rich interfacial film on the negative electrode during the first charge and discharge stage. This layer of interfacial film can significantly increase the penetration and diffusion ability of lithium ions at the negative electrode interface, so it can effectively increase the lithium ion density. Low temperature and rate performance of ion batteries. However, the fluorinated cyclic carbonate compounds will be gradually consumed with the cycle of lithium-ion batteries, and more interfacial films containing LiF will be formed, but components such as LiF will be scattered in the later stage or after long cycles at low temperatures. Regularly piled up on the surface of the negative electrode, as the negative electrode expands, the interfacial film is easily broken, causing a side reaction between the electrolyte and the negative electrode, and making the transition metal ions dissolved from the positive electrode pass through the LiF layer into the negative electrode to block lithium ions from entering the negative electrode. Pores lead to the local formation of "dead lithium", that is, the precipitation of lithium and the "sudden dive" in the later stage of the battery cycle. Based on this, adding cyclic sulfonylimide compounds can form an outer interface film containing a large amount of LiSO 3 , ROSO 2 Li, Li x N y O z , sulfur atoms and oxygen on the positive and negative electrodes during the first charge and discharge stage. Atoms all contain lone pairs of electrons and can attract Li + , thereby speeding up Li + shuttling in the solid electrolyte interface film. The interface film components formed by nitrogen atoms are tough, not easy to break, and have strong high temperature resistance, while the double bonds in the ring can Polymerization to form a "layered" structure of the negative electrode interface film can make LiF and other components evenly dispersed on the surface of the negative electrode, so that the transition metal ions dissolved from the positive electrode cannot enter the interior of the negative electrode and cause the battery to "suddenly dive". In general, the combination of the two can effectively avoid the further consumption of a single fluorinated cyclic carbonate compound in the electrolyte and the reaction between the electrolyte and the negative electrode interface, thus greatly enhancing the high temperature and cycle performance of the lithium-ion battery. The combination of these additives can enhance the high-temperature cycle performance, normal-temperature cycle performance, low-temperature discharge performance and rate performance of the lithium-ion battery while inhibiting its lithium precipitation.
优选的，环状磺酰亚胺类化合物的结构式中M
+优选为Li
+、K
+、Cs
+，R
1优选为H或C
1-C
3的烷基。环状磺酰亚胺类化合物于所述非水电解液中的质量百分比为0.1～0.5％，具体可但不限于为0.1％、0.2％、0.3％、0.4％、0.5％，环状磺酰亚胺类化合物选自化合物A至化合物E中的至少一种，
Preferably, in the structural formula of the cyclic sulfonimide compound, M + is preferably Li + , K + , Cs + , and R 1 is preferably H or a C 1 -C 3 alkyl group. The mass percentage of cyclic sulfonimide compounds in the non-aqueous electrolyte is 0.1-0.5%, specifically but not limited to 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, cyclic sulfonyl The imine compound is selected from at least one of compound A to compound E,
其中，化合物A合成方法如下：Wherein, compound A synthesis method is as follows:
化合物E合成方法如下：Compound E synthetic method is as follows:
化合物C采用化合物A类似的合成方法，其差别在于用CsOH替换LiOH。 化合物A、化合物C和化合物E皆可采用化合物B为原料进行反应可得。Compound C was synthesized similarly to Compound A, with the difference that LiOH was replaced by CsOH. Compound A, Compound C and Compound E can all be obtained by reacting Compound B as a raw material.
优选的，氟代环状碳酸酯类化合物于非水电解液中的质量百分比为0.5～10％，具体可但不限于为0.5％、0.7％、0.9％、1.0％、1.2％、1.5％、2.0％、2.3％、2.5％、3.0％、3.5％、3.8％、4.3％、5.0％、5.7％、6.0％、7.0％、8.0％、8.5％、9.0％、9.3％、9.6％、10％。Preferably, the mass percentage of the fluorinated cyclic carbonate compound in the non-aqueous electrolyte is 0.5-10%, specifically but not limited to 0.5%, 0.7%, 0.9%, 1.0%, 1.2%, 1.5%, 2.0%, 2.3%, 2.5%, 3.0%, 3.5%, 3.8%, 4.3%, 5.0%, 5.7%, 6.0%, 7.0%, 8.0%, 8.5%, 9.0%, 9.3%, 9.6%, 10% .
优选的，锂盐选自六氟磷酸锂(LiPF
6)、二氟磷酸锂(LiPO
2F
2)、双草酸硼酸锂(C
4BLiO
8)、二氟草酸硼酸锂(C
2BF
2LiO
4)、二氟二草酸磷酸锂(LiDFBP)、四氟硼酸锂(LiBF
4)、四氟草酸磷酸锂(LiPF
4C
2O
4)、双三氟甲基磺酰亚胺锂(LiN(CF
3SO
2)
2)和双氟磺酰亚胺锂(LiFSI)中的至少一种，上述锂盐在非水电解液中的浓度为0.5～2.5mol/L。优选的，锂盐为LiPF
6或者LiPF
6与其他锂盐的混合物。
Preferably, the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ), lithium difluorophosphate (LiPO 2 F 2 ), lithium bisoxalate borate (C 4 BLiO 8 ), lithium difluorooxalate borate (C 2 BF 2 LiO 4 ), di Lithium fluorodioxalate phosphate (LiDFBP), lithium tetrafluoroborate (LiBF 4 ), lithium tetrafluorooxalate phosphate (LiPF 4 C 2 O 4 ), lithium bistrifluoromethanesulfonimide (LiN(CF 3 SO 2 ) 2 ) and at least one of lithium bisfluorosulfonyl imide (LiFSI), the concentration of the lithium salt in the non-aqueous electrolyte is 0.5-2.5 mol/L. Preferably, the lithium salt is LiPF 6 or a mixture of LiPF 6 and other lithium salts.
优选的，非水有机溶剂选自碳酸乙烯酯(EC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸丙烯酯(PC)、乙酸乙酯(Ea)、乙酸丁酯(n-Ba)、γ-丁内酯(γ-Bt)、丙酸丙酯(n-Pp)、丙酸乙酯(EP)和丁酸乙酯(Eb)中的至少一种。Preferably, the non-aqueous organic solvent is selected from ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC), ethyl acetate (Ea), butyl acetate (n-Ba), γ-butyrolactone (γ-Bt), propyl propionate (n-Pp), ethyl propionate (EP) and ethyl butyrate (Eb) at least one of .
本申请的二次电池，包括正极、负极、电解液和用于隔离所述正极和所述负极的隔膜，电解液为前述的非水电解液。本申请的二次电池的非水电解液的添加剂包括环状磺酰亚胺类化合物与氟代环状碳酸酯类化合物，可使二次电池具有优异的高温循环性能、常温循环性能、倍率性能和低温放电性能，且能有效避免低温析锂，故可满足高能量密度、高电压的三元材料电池的使用要求。The secondary battery of the present application includes a positive electrode, a negative electrode, an electrolyte and a separator for isolating the positive electrode and the negative electrode, and the electrolyte is the aforementioned non-aqueous electrolyte. The additives of the non-aqueous electrolyte of the secondary battery of the present application include cyclic sulfonimide compounds and fluorinated cyclic carbonate compounds, which can make the secondary battery have excellent high-temperature cycle performance, normal temperature cycle performance, and rate performance And low-temperature discharge performance, and can effectively avoid low-temperature lithium precipitation, so it can meet the requirements of high-energy density, high-voltage ternary material batteries.
优选的，正极的活性材料为LiNi
xCo
yMn
zM
(1-x-y-z)O
2或LiNi
xCo
yAl
zN
(1-x-y-z)O
2，其中，M为Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V和Ti中的任意一种，N为Mn、Mg、Cu、Zn、Sn、B、Ga、Cr、Sr、V和Ti中的任意一种，0.5<x<1，0<y≤1，0<z≤1，x+y+z≤1，且最高充电电压为4.35～4.5V。负极的活性材料选自人造石墨、天然石墨、钛酸锂、硅碳复合材料和氧化亚硅中的至少一种。
Preferably, the positive active material is LiNixCoyMnzM (1- xyz ) O2 or LiNixCoyAlzN ( 1- xyz ) O2 , wherein M is Mg, Cu, Zn, Al, Any one of Sn, B, Ga, Cr, Sr, V and Ti, N is any one of Mn, Mg, Cu, Zn, Sn, B, Ga, Cr, Sr, V and Ti, 0.5<x<1,0<y≤1,0<z≤1, x+y+z≤1, and the highest charging voltage is 4.35-4.5V. The active material of the negative electrode is at least one selected from artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material and silicon oxide.
下面通过具体实施例来进一步说明本申请的目的、技术方案及有益效果， 但不构成对本申请的任何限制。实施例中未注明具体条件者，可按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可通过市售购买获得的常规产品或前述说明的合成方法而获得。The purpose, technical solutions and beneficial effects of the present application will be further described below through specific examples, but this does not constitute any limitation to the present application. Those who do not indicate specific conditions in the examples can be carried out according to conventional conditions or conditions suggested by the manufacturer. The reagents or instruments used, whose manufacturers were not indicated, were obtained from commercially available conventional products or the synthetic methods described above.
实施例1Example 1
(1)锂离子电池非水电解液的制备：在充满氮气的手套箱(O
2＜2ppm，H
2O＜3ppm)中，将碳酸二甲酯(EC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、按照质量比1:1:1混合均匀，制得非水有机溶剂86.2g，加入0.3g化合物A、1g化合物F。将溶液密封打包放置急冻间(-4℃)冷冻2h之后取出，在充满氮气的手套箱(O
2＜2ppm，H
2O＜3ppm)中，向混合溶液中缓慢加入12.5g六氟磷酸锂，混合均匀后即制成锂离子电池非水电解液。
(1) Preparation of non-aqueous electrolyte for lithium-ion batteries: In a nitrogen-filled glove box (O 2 <2ppm, H 2 O<3ppm), dimethyl carbonate (EC), diethyl carbonate (DEC), Ethyl methyl carbonate (EMC) was mixed uniformly according to the mass ratio of 1:1:1 to obtain 86.2 g of non-aqueous organic solvent, and 0.3 g of compound A and 1 g of compound F were added. Seal the solution and place it in the freezer (-4°C) for 2 hours, then take it out, and slowly add 12.5g of lithium hexafluorophosphate to the mixed solution in a nitrogen-filled glove box (O 2 <2ppm, H 2 O<3ppm), and mix well Afterwards, the non-aqueous electrolyte for lithium-ion batteries is made.
(2)正极的制备：将镍钴锰酸锂三元材料LiNi
0.6Mn
0.2Co
0.2O
2、粘接剂PVDF和导电剂SuperP按质量比97.5:1.5:1混合均匀制成一定粘度的锂离子电池正极浆料，将混制的浆料涂布在铝箔的两面后，烘干、辊压后得到正极片。
(2) Preparation of the positive electrode: LiNi 0.6 Mn 0.2 Co 0.2 O 2 ternary material LiNi 0.6 Mn 0.2 Co 0.2 O 2 , binder PVDF and conductive agent SuperP are uniformly mixed at a mass ratio of 97.5:1.5:1 to make lithium ions with a certain viscosity The positive electrode slurry of the battery, after coating the mixed slurry on both sides of the aluminum foil, drying and rolling to obtain the positive electrode sheet.
(3)负极的制备：将人造石墨与导电剂SuperP、增稠剂CMC、粘接剂SBR(丁苯橡胶乳液)按质量比95:1:1.5:2.5的比例制成浆料，混合均匀，用混制的浆料涂布在铜箔的两面后，烘干、辊压后得到负极片。(3) Preparation of negative electrode: make artificial graphite and conductive agent SuperP, thickener CMC, and adhesive SBR (styrene-butadiene rubber emulsion) into a slurry in a mass ratio of 95:1:1.5:2.5, mix evenly, The mixed slurry is coated on both sides of the copper foil, dried and rolled to obtain a negative electrode sheet.
(4)锂离子电池的制备：将正极、隔膜以及负极以叠片的方式制成方形电芯，采用聚合物包装，灌装上述制备的锂离子电池非水电解液，经化成、分容等工序后制成容量为2000mAh的锂离子电池。(4) Preparation of lithium-ion battery: the positive electrode, diaphragm and negative electrode are stacked into square batteries, packed in polymer, filled with the non-aqueous electrolyte of lithium-ion battery prepared above, and processed by chemical formation, volume separation, etc. After the process, a lithium-ion battery with a capacity of 2000mAh is made.
实施例2～8和对比例1～3的电解液配方如表1所示，配制电解液的步骤同The electrolyte formulations of Examples 2 to 8 and Comparative Examples 1 to 3 are as shown in Table 1, and the steps for preparing the electrolyte are the same
实施例1。Example 1.
表1各实施例的电解液组分The electrolyte composition of each embodiment of table 1
对实施例1～8和对比例1～3制成的锂离子电池分别进行常温循环性能、高温循环性能、低温放电测试、高倍率放电测试和低温析锂测试，具体测试条件如下，性能测试结果如表2所示。The lithium-ion batteries made in Examples 1-8 and Comparative Examples 1-3 were respectively subjected to normal temperature cycle performance, high temperature cycle performance, low-temperature discharge test, high-rate discharge test and low-temperature lithium analysis test. The specific test conditions are as follows, and the performance test results As shown in table 2.
(1)常温循环性能测试：(1) Normal temperature cycle performance test:
将锂离子电池置于25℃的环境中，以1C的电流恒流充电至4.5V然后恒压充电至电流下至0.05C，然后以1C的电流恒流放电至3.0V，如此循环，记录第一圈的放电容量和最后一圈的放电容量。计算公式如下：Put the lithium-ion battery in an environment of 25°C, charge it with a constant current of 1C to 4.5V, then charge it with a constant voltage until the current drops to 0.05C, and then discharge it with a constant current of 1C to 3.0V, and cycle like this, record the first The discharge capacity of one lap and the discharge capacity of the last lap. Calculated as follows:
容量保持率＝最后一圈的放电容量/第一圈的放电容量×100％。Capacity retention = discharge capacity of the last cycle/discharge capacity of the first cycle × 100%.
(2)高温循环性能测试：(2) High temperature cycle performance test:
将电池置于恒温45℃的烘箱中，以1C的电流恒流充电至4.5V然后恒压充电至电流下至0.05C，然后以1C的电流恒流放电至3.0V，如此循环，记录第一圈的放电容量和最后一圈的放电容量以及第一周电池厚度和最后一周电池厚度计算公式如下：Put the battery in an oven with a constant temperature of 45°C, charge it with a constant current of 1C to 4.5V, then charge it with a constant voltage until the current drops to 0.05C, and then discharge it with a constant current of 1C to 3.0V, and cycle like this, record the first The discharge capacity of the first cycle and the discharge capacity of the last cycle, as well as the battery thickness of the first cycle and the battery thickness of the last cycle are calculated as follows:
容量保持率＝最后一圈的放电容量/第一圈的放电容量×100％。Capacity retention = discharge capacity of the last cycle/discharge capacity of the first cycle × 100%.
(3)低温放电测试：(3) Low temperature discharge test:
将化成后的电池在常温下1C恒流恒压充电至4.5V，然后将电池置于-20℃低温环境中搁置4小时，以0.5C放电至3.0V，测量电池的容量保持率。计算公式如下：Charge the formed battery at 1C constant current and constant voltage to 4.5V at room temperature, then place the battery in a low-temperature environment of -20°C for 4 hours, discharge it at 0.5C to 3.0V, and measure the capacity retention of the battery. Calculated as follows:
电池容量保持率(％)＝保持容量/初始容量×100％。Battery capacity retention rate (%)=retention capacity/initial capacity×100%.
(4)3C高倍率放电测试：(4) 3C high rate discharge test:
将锂离子电池置于25℃的环境中，以1C的电流恒流充电至4.5V然后恒压充电至电流下至0.05C，然后以3C的电流恒流放电至3.0V，测量电池的容量保持率。计算公式如下：Put the lithium-ion battery in an environment of 25°C, charge it with a constant current of 1C to 4.5V, then charge it with a constant voltage until the current drops to 0.05C, and then discharge it with a constant current of 3C to 3.0V, and measure the capacity retention of the battery Rate. Calculated as follows:
电池容量保持率(％)＝保持容量/初始容量×100％。Battery capacity retention rate (%)=retention capacity/initial capacity×100%.
(5)低温析锂测试：(5) Low temperature lithium analysis test:
将锂离子电池置于恒温-10℃的烘箱中，以0.5C的电流恒流充电至4.5V然后恒压充电至电流下至0.05C，然后以0.5C的电流恒流放电至3.0V，如此循环40周，拆解电池，观察锂离子电池负极表面析锂情况。Put the lithium-ion battery in an oven at a constant temperature of -10°C, charge it with a constant current of 0.5C to 4.5V, then charge it with a constant voltage until the current drops to 0.05C, and then discharge it with a constant current of 0.5C to 3.0V, so Cycle for 40 cycles, disassemble the battery, and observe the lithium-ion battery negative electrode surface lithium precipitation.
表2锂离子电池性能测试结果Table 2 Li-ion battery performance test results
由表2的结果可知，将环状磺酰亚胺类化合物与氟代环状碳酸酯类化合物两种添加剂相结合，不仅可提高二次电池的高温循环性能、常温循环性能、倍率性能和低温放电性能，更重要的是能有效避免低温析锂。这是由于环状磺酰亚胺类化合物可在首次充放电阶段在正极和负极形成含大量LiSO
3、ROSO
2Li、Li
xN
yO
z的外层界面膜，硫原子和氧原子由于皆含有孤对电子进而可吸引Li
+，从而加快Li
+在固体电解质界面膜中穿梭，氮原子形成的界面膜组分富有韧性，不易破裂、耐高温性能强，而环内双键能聚合形成“层状”结构的负极界面膜，可使得LiF等组分均匀分散在负极表面，进而使得正极溶出的过渡金属离子不能进入负极内部而引发电池“突然跳水”。而对比例2虽然含有环状磺酰亚胺类化合物，其形成的界面膜能抑制析锂且稳定性高，且能于一定程度上改善循环性能，但是导电子能力不佳，故低温和放电性能较差。对比例3中的氟代环状碳酸酯类化合物可在首次充放电阶段于负极形成富含LiF的界面膜，该层界面膜能明显增加锂离子在负极界面的穿透与扩散能力，故而能增加锂离子电池的低温与倍率性能，但是经循环到后期或在低温条件下长循环后，其析锂问题无法得到解决。
From the results in Table 2, it can be seen that the combination of cyclic sulfonimide compounds and fluorinated cyclic carbonate compounds can not only improve the high-temperature cycle performance, normal temperature cycle performance, rate performance and low-temperature cycle performance of the secondary battery. Discharge performance, more importantly, can effectively avoid low-temperature lithium precipitation. This is because cyclic sulfonylimide compounds can form an outer interface film containing a large amount of LiSO 3 , ROSO 2 Li, and Li x N y O z on the positive and negative electrodes during the first charge and discharge stage. Containing lone pairs of electrons can attract Li + , thereby speeding up the shuttling of Li + in the solid electrolyte interface film. The interface film components formed by nitrogen atoms are tough, not easy to break, and have strong high temperature resistance, while the double bonds in the ring can be polymerized to form " The layered structure of the negative electrode interface film can make LiF and other components evenly dispersed on the surface of the negative electrode, so that the transition metal ions dissolved from the positive electrode cannot enter the interior of the negative electrode and cause the battery to "suddenly dive". Although comparative example 2 contains a cyclic sulfonimide compound, the interfacial film formed by it can inhibit lithium precipitation and has high stability, and can improve the cycle performance to a certain extent, but the ability to conduct electrons is not good, so low temperature and discharge Performance is poor. The fluorinated cyclic carbonate compound in Comparative Example 3 can form a LiF-rich interfacial film on the negative electrode during the first charge and discharge stage. This layer of interfacial film can significantly increase the penetration and diffusion ability of lithium ions at the negative electrode interface, so it can Increase the low-temperature and rate performance of lithium-ion batteries, but after cycling to the later stage or long-term cycling under low temperature conditions, the problem of lithium precipitation cannot be solved.
最后应当说明的是，以上实施例仅用以说明本申请的技术方案而非对本申请保护范围的限制，尽管参照较佳实施例对本申请作了详细说明，本领域的普通技术人员应当理解，可以对本申请的技术方案进行修改或者等同替换，而不脱离本申请技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application rather than limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that Modifications or equivalent replacements are made to the technical solutions of the present application without departing from the essence and scope of the technical solutions of the present application.
Claims (9)
- 一种非水电解液包括锂盐、非水有机溶剂和添加剂，其特征在于，所述添加剂包括环状磺酰亚胺类化合物和氟代环状碳酸酯类化合物，所述环状磺酰亚胺类化合物的结构式为结构式1或结构式2，所述氟代环状碳酸酯类化合物的结构式为结构式3、结构式4或结构式5，A kind of non-aqueous electrolytic solution comprises lithium salt, non-aqueous organic solvent and additive, is characterized in that, described additive comprises cyclic sulfonyl imide compound and fluorinated cyclic carbonate compound, and described cyclic sulfonyl imide The structural formula of the amine compound is structural formula 1 or structural formula 2, and the structural formula of the fluorinated cyclic carbonate compound is structural formula 3, structural formula 4 or structural formula 5,
其中，M +为Li +、Na +、K +、Cs +，R 1为H或烷基。 Wherein, M + is Li + , Na + , K + , Cs + , and R 1 is H or an alkyl group. - 如权利要求1所述的非水电解液，其特征在于，M +为Li +、K +、Cs +，R 1为H或C 1-C 3的烷基。 The non-aqueous electrolytic solution according to claim 1, wherein M + is Li + , K + , Cs + , and R 1 is H or C 1 -C 3 alkyl.
- 如权利要求1所述的非水电解液，其特征在于，所述环状磺酰亚胺类化合物于所述非水电解液中的质量百分比为0.1～0.5％，所述氟代环状碳酸酯类化合物于所述非水电解液中的质量百分比为0.5～10％。The non-aqueous electrolytic solution according to claim 1, wherein the mass percentage of the cyclic sulfonimide compound in the non-aqueous electrolytic solution is 0.1-0.5%, and the fluorinated cyclic carbonic acid The mass percentage of the ester compound in the non-aqueous electrolytic solution is 0.5-10%.
- 如权利要求1所述的非水电解液，其特征在于，所述环状磺酰亚胺类化合物选自化合物A至化合物E中的至少一种，The non-aqueous electrolytic solution according to claim 1, wherein the cyclic sulfonimide compound is selected from at least one of compound A to compound E,
- 如权利要求1所述的非水电解液，其特征在于，所述锂盐选自六氟磷酸锂、二氟磷酸锂、双草酸硼酸锂、二氟草酸硼酸锂、二氟草酸磷酸锂、四氟硼酸锂、四氟草酸磷酸锂、双三氟甲基磺酰亚胺锂和双氟磺酰亚胺锂中的至少一种。The non-aqueous electrolytic solution according to claim 1, wherein the lithium salt is selected from lithium hexafluorophosphate, lithium difluorophosphate, lithium bisoxalate borate, lithium difluorooxalate borate, lithium difluorooxalate phosphate, lithium tetrafluoroborate , at least one of lithium tetrafluorooxalate phosphate, lithium bistrifluoromethylsulfonyl imide and lithium bisfluorosulfonyl imide.
- 如权利要求1所述的非水电解液，其特征在于，所述非水有机溶剂选自碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸丙烯酯、乙酸乙酯、乙酸丁酯、γ-丁内酯、丙酸丙酯、丙酸乙酯和丁酸乙酯中的至少一种。The non-aqueous electrolytic solution according to claim 1, wherein the non-aqueous organic solvent is selected from ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethyl acetate , at least one of butyl acetate, γ-butyrolactone, propyl propionate, ethyl propionate and ethyl butyrate.
- 一种二次电池，包括正极、负极、电解液和用于隔离所述正极和所述负极的隔膜，其特征在于，所述电解液为权利要求1～6任一所述的非水电解液。A secondary battery, comprising a positive electrode, a negative electrode, an electrolyte, and a diaphragm for isolating the positive electrode and the negative electrode, wherein the electrolyte is the non-aqueous electrolyte according to any one of claims 1 to 6 .
- 如权利要求7所述的二次电池，其特征在于，所述正极的活性材料为LiNi xCo yMn zM (1-x-y-z)O 2或LiNi xCo yAl zN (1-x-y-z)O 2，其中，M为Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V和Ti中的任意一种，N为Mn、Mg、Cu、Zn、Sn、B、Ga、Cr、Sr、V和Ti中的任意一种，0.5<x<1，0<y≤1，0<z≤1，x+y+z≤1。 The secondary battery according to claim 7, wherein the active material of the positive electrode is LiNixCoyMnzM (1- xyz ) O2 or LiNixCoyAlzN ( 1 - xyz ) O 2 , where M is any one of Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, and N is Mn, Mg, Cu, Zn, Sn, B, Ga, Cr , any one of Sr, V and Ti, 0.5<x<1, 0<y≤1, 0<z≤1, x+y+z≤1.
- 如权利要求7所述的二次电池，其特征在于，所述负极的活性材料选自人造石墨、天然石墨、钛酸锂、硅碳复合材料和氧化亚硅中的至少一种。The secondary battery according to claim 7, wherein the active material of the negative electrode is selected from at least one of artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material and silicon oxide.
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