CN116365034A - Nonaqueous electrolyte and lithium ion battery - Google Patents
Nonaqueous electrolyte and lithium ion battery Download PDFInfo
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- CN116365034A CN116365034A CN202310475177.6A CN202310475177A CN116365034A CN 116365034 A CN116365034 A CN 116365034A CN 202310475177 A CN202310475177 A CN 202310475177A CN 116365034 A CN116365034 A CN 116365034A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 229940126062 Compound A Drugs 0.000 claims abstract description 14
- 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 abstract description 14
- -1 cyclic sulfone imine Chemical class 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical class [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000005678 chain carbonates Chemical class 0.000 claims description 3
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate 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
- 239000011572 manganese Substances 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 125000006657 (C1-C10) hydrocarbyl group Chemical group 0.000 claims description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910013716 LiNi Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 230000037427 ion transport Effects 0.000 abstract description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003860 storage Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000007774 longterm Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002562 thickening agent 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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
- H01M2300/0037—Mixture of solvents
-
- 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
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a non-aqueous electrolyte and a lithium ion battery. The nonaqueous electrolyte comprises a nonaqueous organic solvent, an electrolyte salt and an additive, wherein the additive comprises a compound A. The structural formula of the compound A is shown as a structural formula I, a structural formula II or a structural formula III. The compound A in the nonaqueous electrolyte of the present invention contains a cyclic sulfone imine and a cyclic imide structure which are connected to each other, and can form a stable interfacial film at the interface. First, the film has good lithium ion transport channels, so that channel collapse is not generated in the circulating process, and circulating and low-temperature performances are improved. Secondly, the interface of the positive electrode and the electrolyte can be optimized by forming a stable interface film, the surface activity of the positive electrode is reduced, and the oxidative decomposition of the electrolyte is inhibited, so that the high-low temperature and the cycle performance of the battery are improved, and the method is particularly used for improving the high-low temperature and the cycle performance of a high-voltage (4.4V) high-nickel ternary lithium ion battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a nonaqueous electrolyte and a lithium ion battery.
Background
With the continuous increase of the capacity requirements of secondary batteries, such as pure electric vehicles, hybrid electric vehicles, portable energy storage devices, and the like, it is expected to develop secondary batteries with higher energy density and power density to realize energy storage and long-term endurance.
In addition to improvements in existing materials and battery fabrication processes, high voltage (4.35-5V) ternary positive electrode materials are one of the popular research directions to achieve high energy density of batteries by increasing the depth of charge of the positive electrode active material. Among them, the high nickel ternary positive electrode material (nickel content is not less than 0.6) is a relatively common positive electrode material due to its higher capacity. However, the high-nickel ternary material is easy to generate irreversible phase change of H2-H3 at high voltage and high temperature, and oxygen is precipitated, so that the interface between electrolyte and an electrode is unstable, and the battery is subjected to the problems of poor high-temperature storage and serious cyclic gas production. Meanwhile, the conventional carbonate electrolyte can be oxidized and decomposed on the surface of the positive electrode material of the battery under the high voltage of 4.4V, and particularly under the high temperature condition, the oxidation and decomposition of the electrolyte can be accelerated, so that the positive electrode material is subjected to degradation reaction.
Therefore, it is necessary to develop an electrolyte capable of withstanding a high voltage of 4.4V and further achieving excellent performance of lithium ion batteries.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a nonaqueous electrolyte solution and a lithium ion battery, in which the compound a contained in the additive can reduce the surface activity of the positive electrode material to suppress oxidative decomposition of the electrolyte solution, so as to improve the high-temperature storage and cycle performance of the high-voltage (4.4V) lithium ion battery (particularly, a high-nickel ternary material system).
To achieve the above object, a first aspect of the present invention provides a nonaqueous electrolytic solution comprising a nonaqueous organic solvent, an electrolyte salt and an additive, the additive comprising a compound a. The structural formula of the compound A is shown as a structural formula I, a structural formula II or a structural formula III.
Wherein R is 1 ～R 3 Each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C10 hydrocarbyl, substituted or unsubstituted phosphonate, R 4 ～R 5 Each independently selected from hydrogen, substituted or unsubstituted C1-C6 alkyl.
The compound A in the nonaqueous electrolyte of the present invention contains a cyclic sulfone imine and a cyclic imide structure which are connected to each other, and can form a stable interfacial film at the interface. First, the film has good lithium ion transport channels, so that channel collapse is not generated in the circulating process, and circulating and low-temperature performances are improved. Secondly, the interface of the positive electrode and the electrolyte can be optimized by forming a stable interface film, the surface activity of the positive electrode is reduced, and the oxidative decomposition of the electrolyte is inhibited, so that the high-low temperature and the cycle performance of the battery are improved, and the method is particularly used for improving the high-low temperature and the cycle performance of a high-voltage (4.4V) high-nickel ternary lithium ion battery.
As one embodiment of the present invention, R 1 ～R 3 Each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phosphonate, R 4 ～R 5 Each independently selected from hydrogen, substituted or unsubstituted C1-C3 alkyl. Preferably, R 1 ～R 3 At least one of the electrolyte interface film is phosphonate, the stability of the SEI film can be improved by introducing phosphonate, P, O and other elements enrich the components of the electrode/electrolyte interface film, and the structural stability of the interface film is further improved, so that the high-temperature storage performance of the lithium ion battery is improved.
Wherein P is connected with 3O on the group of phosphonate, the structural formula is as follows, R 6 、R 7 May be hydrogen or a substituted or unsubstituted C1-C10 hydrocarbon group.
As one embodiment of the present invention, compound A is at least one of compounds I to VI.
As a technical scheme of the invention, the compound A accounts for 0.1-5.0% of the sum of the mass of the nonaqueous organic solvent, the electrolyte salt and the additive. Preferably, the compound A accounts for 0.1 to 2.0% of the sum of the mass of the nonaqueous organic solvent, the electrolyte salt and the additive. As an example, the proportion of compound a to the sum of the mass of the nonaqueous organic solvent, the electrolyte salt, and the additive may be, but is not limited to, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%.
As a technical scheme of the invention, the electrolyte salt accounts for 6-15% of the sum of the mass of the nonaqueous organic solvent, the electrolyte salt and the additive. Preferably, the electrolyte salt is 8-15%. As an example, the electrolyte salt may be 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% in ratio, but is not limited to. The electrolyte salt is selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium triflate (LiCF) 3 SO 3 ) Lithium bis (trifluoromethylsulfonyl) imide (LiN (CF) 3 SO 2 ) 2 ) Lithium dioxalate borate (C) 4 BLiO 8 ) Lithium difluorooxalato borate (C) 2 BF 2 LiO 4 ) Lithium difluorophosphate (LiPO) 2 F 2 ) At least one of lithium difluorobis (oxalato) phosphate (LiDFBP), lithium difluorosulfonimide (LiFSI), and lithium bistrifluoromethylsulfonimide (LiTFSI).
As an embodiment of the present invention, the nonaqueous organic solvent is at least one of a chain carbonate, a cyclic carbonate and a carboxylic acid ester. Preferably, the nonaqueous organic solvent is a mixture of a chain carbonate and a cyclic carbonate. As an example, the nonaqueous organic solvent is selected from at least one of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), propylene Carbonate (PC), butyl acetate (n-Ba), γ -butyrolactone (γ -Bt), propyl propionate (n-Pp), ethyl Propionate (EP), and ethyl butyrate (Eb). The non-aqueous organic solvent accounts for more than or equal to 80 percent, preferably more than or equal to 85 percent of the sum of the mass of the non-aqueous organic solvent, the electrolyte salt and the additive. By way of example, the nonaqueous organic solvent may be, but is not limited to, 80% > or more, 81% > or more, 82% > or more, 83% > or more, 84% > or more, 85% > or more, 86% > or more, 87% > or more, 88% > or more, 89% > or more, 90% or more, based on the sum of the nonaqueous organic solvent, electrolyte salt, and additive mass.
As an embodiment of the present invention, the additive further comprises a compound B. The compound B is at least one selected from Vinylene Carbonate (VC), ethylene carbonate (VEC), fluoroethylene carbonate (FEC), ethylene Sulfite (ES), 1, 3-Propane Sultone (PS), tris (trimethylsilane) phosphate (TMSP), and ethylene sulfate (DTD). The compound B accounts for 0.1 to 10.0 percent of the sum of the mass of the nonaqueous organic solvent, the electrolyte salt and the additive. Preferably, the compound B accounts for 0.1 to 6.0% of the sum of the mass of the nonaqueous organic solvent, the electrolyte salt and the additive. As an example, the proportion of compound B to the sum of the mass of the nonaqueous organic solvent, the electrolyte salt, and the additive may be, but is not limited to, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%.
The second aspect of the present invention provides a lithium ion battery comprising a positive electrode material, a negative electrode material, and a nonaqueous electrolyte. The lithium ion battery has better cycle life and high-temperature storage performance, and is favorable for further industrialized development of the lithium ion battery.
As a technical scheme of the invention, the positive electrode material is nickel cobalt manganese oxide material. The chemical formula of the nickel cobalt manganese oxide material is LiNi x Co y Mn (1-x-y) M z O 2 ，0.6≤x≤0.9，x+y<1，0≤z<0.08, M is one of Al, mg, zr and Ti. Preferably x=0.6, y=0.2, m is Zr, z=0.03, or x=0.8, y=0.1, m is Zr, z=0.02.
As an aspect of the present invention, the anode material is selected from at least one of a carbon-based anode material, a titanium-based oxide anode material, and a silicon-based anode material.
As an aspect of the present invention, the negative electrode material may be selected from artificial graphite, natural graphite, hard carbon, soft carbon, lithium titanate, si material, silicon oxygen material, or silicon carbon material (10 wt.% Si).
Detailed Description
For a better description of the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention and should not be taken as limiting the present invention.
Wherein, the specific conditions are not noted in the examples, and the method can be carried out according to the conventional conditions or the conditions suggested by manufacturers. The reagents or apparatus used were conventional products available commercially without the manufacturer's attention.
Example 1
(1) Preparation of nonaqueous electrolyte: preparing an electrolyte in a vacuum glove box with the moisture content less than 1ppm under the argon atmosphere, mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) according to the weight ratio of EC to DEC to EMC=1 to 1 in the dry argon atmosphere glove box, adding the compound I, dissolving and fully stirring, adding lithium hexafluorophosphate, and uniformly mixing to obtain the electrolyte.
(2) Preparation of positive electrode: liNi is added to 0.6 Co 0.2 Mn 0.2 Zr 0.03 O 2 Uniformly mixing the adhesive PVDF and the conductive agent SuperP according to the mass ratio of 97:1:2 to prepare lithium ion battery anode slurry with certain viscosity, coating the mixed slurry on two sides of an aluminum foil, and drying and rolling to obtain the anode plate.
(3) Preparation of the negative electrode: preparing a silicon-carbon anode material (10 wt.% Si), a conductive agent SuperP, a thickener CMC and an adhesive SBR (styrene butadiene rubber emulsion) into slurry according to the mass ratio of 96:1:1:2, uniformly mixing, coating the mixed slurry on two sides of a copper foil, and drying and rolling to obtain the anode sheet.
(4) Preparation of a lithium ion battery: and (3) preparing the positive plate, the diaphragm and the negative plate into square battery cells in a lamination mode, packaging by adopting polymers, filling the prepared lithium ion battery nonaqueous electrolyte, and preparing the lithium ion battery with the capacity of 1400mAh through the procedures of formation, capacity division and the like.
The electrolyte formulations of examples 1 to 16 and comparative examples 1 to 7 are shown in Table 1, and the procedure for preparing the electrolytes and preparing the batteries of examples 2 to 16 and comparative examples 1 to 7 are the same as in example 1.
Table 1 electrolyte components of examples and comparative examples
The lithium ion batteries manufactured in examples 1 to 16 and comparative examples 1 to 7 were subjected to a normal temperature cycle test, a high temperature storage test, and a low temperature discharge test, respectively, under the following specific test conditions, and the test results are shown in table 2.
(1) Normal temperature cycle test
Lithium ion batteries were charged and discharged at 1.0C/1.0C at normal temperature (25 ℃) and the upper limit voltage was 4.4V (the battery discharge capacity was C0), and then charged and discharged at 1.0C/1.0C at normal temperature for 500 weeks (the battery discharge capacity was C1).
Capacity retention= (C1/C0) ×100%.
(2) High temperature cycle test of lithium ion battery
Charging and discharging the lithium ion battery at 1.0C/1.0C (the discharge capacity of the battery is C0) at an excessively high temperature (45 ℃) with an upper limit voltage of 4.4V, then charging and discharging the lithium ion battery at 1.0C/1.0C for 500 weeks (the discharge capacity of the battery is C1) at normal temperature,
capacity retention = (C1/C0) ×100%
(3) High temperature storage test
Lithium ion batteries were charged and discharged at 0.3C/0.3C once (the discharge capacity of the battery was recorded as C) at normal temperature (25 ℃ C.) 0 ) The upper limit voltage is 4.4V. Placing the battery in a 60 ℃ oven for 15d, taking out the battery, placing the battery in a 25 ℃ environment, discharging at 0.3C, and recording the discharge capacity as C 1 . The lithium ion battery was then charged and discharged once at 0.3C/0.3C (the discharge capacity of the battery was recorded as C) 2 )。
Capacity retention= (C 1 /C 0 )*100％
Capacity recovery rate= (C 2 /C 0 )*100％
Low temperature discharge test
Lithium ion batteries were charged and discharged at 0.3C/0.3C once (the discharge capacity of the battery was recorded as C) at normal temperature (25 ℃ C.) 0 ) The upper limit voltage is 4.4V. Placing the battery in an oven at-20 ℃ for 4 hours, discharging the battery at 0.3C, and recording the discharge capacity as C 1 The cut-off voltage was 3.0V.
Discharge rate= (C 1 /C 0 )*100％
Table 2 lithium ion battery performance test results
As can be seen from the results of table 2, the use of the compound a of the present invention as an additive can greatly improve the cycle performance, high-temperature storage and low-temperature discharge performance of a battery, since the compound a contains a cyclic sulfonimide and cyclic imide structure connected to each other, an interfacial film which is stable at the interface and has a good lithium ion transport channel can be formed.
Comparative examples 1 to 6 show that the cycle performance, high temperature storage and low temperature discharge performance of the lithium ion battery are better when the content of the compound a is 0.1 to 2.0% of the sum of the mass of the nonaqueous organic solvent, the electrolyte salt and the additive.
Comparative examples 3 and 7 to 10 show that the battery obtained by introducing a phosphonate group into the compound A has better high-temperature storage performance.
Comparative example 3, examples 12 to 16, comparative examples 2 to 6 show that the lithium ion battery performs best when compound B is reintroduced based on compound a, especially when compound B contains both VC and FEC, which may be due to the synergistic effect of VC, FEC and compound a: it is possible that VC forms a polymeric organic layer, FEC forms an inorganic interfacial layer and polymerizes several layers of double-layer interfaces, and compound a forms an inorganic interfacial layer rich in S, N, making up the inorganic SEI hole formed by FEC, and the three synergistically act to form a complete and tough inorganic and organic double interface, improving the electrochemical performance of the battery.
From examples 3, examples 7 to 10 and comparative example 7, it is understood that, although the compound VI of comparative example 7 and the compound A described herein are similar in structure, it is a cyclic sulfonic acid amide, and the structure shown in the present invention is more easily completely consumed to form an electrode electrolyte interface protective layer, as compared with the cyclic sulfone imine of the present application, because its sulfur-oxygen bond energy is greater than the sulfur-nitrogen bond energy. In addition, the stronger oxygen element activity in the compound VI of comparative example 7 is more likely to participate in the interfacial gassing of the battery, which has a negative effect on the battery performance.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A non-aqueous electrolyte comprises a non-aqueous organic solvent, electrolyte salt and an additive, and is characterized in that the additive comprises a compound A, the structural formula of the compound A is shown as a structural formula I, a structural formula II or a structural formula III,
wherein R is 1 ～R 3 Each independently selected from hydrogen, halogen, substituted or unsubstituted C1-C10 hydrocarbyl, substituted or unsubstituted phosphonate, R 4 ～R 5 Each independently selected from hydrogen, substituted or unsubstituted C1-C6 alkyl.
2. The nonaqueous electrolytic solution according to claim 1, wherein R 1 ～R 3 Each independently selected from hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phosphonate, R 4 ～R 5 Each independently selected from hydrogen, substituted or unsubstituted C1-C3 alkyl.
3. The nonaqueous electrolyte according to claim 1, wherein the compound A is at least one of the compounds I to V,
4. the nonaqueous electrolytic solution according to claim 1, wherein the compound a is 0.1 to 5.0% of the sum of the mass of the nonaqueous organic solvent, the electrolyte salt and the additive.
5. The nonaqueous electrolytic solution according to claim 4, wherein the compound A is 0.1 to 2.0% of the sum of the mass of the nonaqueous organic solvent, the electrolyte salt and the additive.
6. The nonaqueous electrolytic solution according to claim 1, wherein the electrolyte salt is at least one selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethylsulfonate, lithium bistrifluoromethylsulfonylimide, lithium dioxaborate, lithium difluorooxalato borate, lithium difluorophosphate, lithium difluorobisoxalato phosphate, lithium bisfluorosulfonyl imide, and lithium bistrifluoromethylsulfonylimide.
7. The nonaqueous electrolytic solution according to claim 1, wherein the nonaqueous organic solvent is at least one selected from the group consisting of a chain carbonate, a cyclic carbonate and a carboxylic acid ester.
8. The nonaqueous electrolytic solution according to claim 1, wherein the additive further comprises a compound B selected from at least one of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, ethylene sulfite, 1, 3-propane sultone, tris (trimethylsilane) phosphate and ethylene sulfate.
9. A lithium ion battery comprising a positive electrode material, a negative electrode material, and the nonaqueous electrolytic solution according to any one of claims 1 to 8.
10. The lithium ion battery of claim 9, wherein the positive electrode material is a nickel cobalt manganese oxide material having a chemical formula LiNi x Co y Mn (1-x-y) M z O 2 ，0.6≤x≤0.9，x+y<1，0≤z<0.08, M is one of Al, mg, zr and Ti.
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