CN117832613A - Nonaqueous electrolyte and lithium ion battery thereof - Google Patents
Nonaqueous electrolyte and lithium ion battery thereof Download PDFInfo
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- CN117832613A CN117832613A CN202311827897.0A CN202311827897A CN117832613A CN 117832613 A CN117832613 A CN 117832613A CN 202311827897 A CN202311827897 A CN 202311827897A CN 117832613 A CN117832613 A CN 117832613A
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- lithium
- lithium ion
- electrolyte
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229940126062 Compound A Drugs 0.000 claims abstract description 7
- 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 7
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 10
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-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
- 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
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-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
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 229940125904 compound 1 Drugs 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 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
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 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
- 239000007784 solid electrolyte Substances 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 125000004434 sulfur atom Chemical group 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ACKHWUITNXEGEP-UHFFFAOYSA-N aluminum cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Co+2].[Ni+2] ACKHWUITNXEGEP-UHFFFAOYSA-N 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 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
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a non-aqueous electrolyte and a lithium ion battery thereof. The nonaqueous electrolyte includes an electrolyte salt, a nonaqueous organic solvent, and an additive. The additive comprises a compound A shown in a structural formula 1. Wherein R is 1 And R is 3 Each independently selected from halogen or C 1 ～C 3 Haloalkyl radicals R of (2) 2 Selected from C 1 ～C 6 A haloalkyl or carbonyl-containing group of (a). In the technical scheme adopted by the invention, the compound A has a halogen substituted disulfonic acid group, has higher oxidation stability and can stably work in a high-voltage (such as 4.5V) lithium ion battery. In addition, the sulfur atoms and substituent atoms are broken, so that a stable and uniform solid electrolyte interface film can be formed on the positive electrode, and the impedance of the lithium ion battery is reduced. At the same time, the halogenated group can form stable and low in the cathodeThe impedance of the solid electrolyte interface film is further reduced, so that the cycle performance of the lithium ion battery is improved.
Description
Technical Field
The invention relates to the technical field of new energy devices, in particular to a nonaqueous electrolyte and a lithium ion battery thereof.
Background
The lithium ion battery is paid attention to because of high energy density, long cycle life and better storage performance, and in order to further deepen the application of the lithium ion battery in the fields of digital products, electric automobiles and aerospace, the pursuit of the market for the lithium ion battery with higher energy density is met, and the effective means for improving the working voltage (4.35-5.00V) of the positive electrode material and reducing the interface impedance in the battery are realized.
However, as the operating voltage of the battery increases, the charge-discharge cycle performance thereof decreases, wherein the electrolyte is decomposed at a high voltage, and a series of side reactions occur, resulting in rapid deterioration of the cycle performance of the battery until failure. Therefore, it is necessary to develop an electrolyte that is suitable for high operating voltage lithium ion batteries to meet the use requirements of high energy density lithium ion batteries.
Disclosure of Invention
In order to solve the problems, the invention provides a nonaqueous electrolyte and a lithium ion battery thereof. The non-aqueous electrolyte has higher oxidation stability, can stably work in a high-voltage lithium ion battery, and can form a stable and low-impedance solid electrolyte interface film on a negative electrode so as to reduce the impedance of the lithium ion battery and improve the cycle performance of the lithium ion battery.
In order to achieve the above object, the present invention provides a nonaqueous electrolytic solution comprising an electrolyte salt, a nonaqueous organic solvent and an additive comprising a compound a represented by structural formula 1,
wherein R is 1 And R is 3 Each independently selected from halogen or C 1 ～C 3 Haloalkyl radicals R of (2) 2 Selected from C 1 ～C 6 A haloalkyl or carbonyl-containing group of (a).
In the technical scheme adopted by the invention, the compound A has a halogen substituted disulfonic acid group, has higher oxidation stability and can stably work in a high-voltage (such as 4.5V) lithium ion battery. In addition, the sulfur atoms and substituent atoms are broken, so that a stable and uniform solid electrolyte interface film can be formed on the positive electrode, and the impedance of the lithium ion battery is reduced. Meanwhile, the halogenated groups can form a stable and low-impedance solid electrolyte interface film on the negative electrode so as to further reduce the impedance of the lithium ion battery and improve the cycle performance of the lithium ion battery.
Preferably, R 1 And R is 3 Each independently selected from fluorine or C 1 ～C 3 R is fluoroalkyl of (2) 2 Selected from C 1 ～C 6 Fluorinated alkyl, C 5 ～C 6 A fluorinated cycloalkyl group or a fluorinated alkanonyl group. When the haloalkyl group is fluoro-substituted, it has lower Li than other haloalkyl groups + Solvating power, which is weak, can increase the anion content in the solvating sheath, thereby enhancing Li + Ability to interact with anions. It will be appreciated that R 2 Selected from C 1 ～C 6 Haloalkyl or carbonyl-containing groups of (a)R is a group of (2) 2 Alkyl groups which may be straight chain, branched or cyclic. The invention is not limited by, as an example, R 2 May be perfluoroethyl, perfluoro-n-butyl, perfluorocyclopentyl.
Preferably, the mass ratio of the compound a is 0.05 to 5.00% based on 100% of the sum of the mass of the electrolyte salt, the nonaqueous organic solvent and the additive. Further, the mass ratio of the compound A may be 0.05 to 3.0%, or 0.50 to 2.00%. By way of example, it may be, but is not limited to, 0.05%, 0.50%, 1.00%, 1.50%, 2.00%, 2.50%, 3.00%, 3.50%, 4.00%, 4..50%, 5.00%.
Preferably, the compound a is selected from at least one of the compounds 1 to 9.
Preferably, the electrolyte salt accounts for 5 to 20% by mass based on 100% by mass of the sum of the electrolyte salt, the nonaqueous organic solvent and the additive. Further, the electrolyte salt is 8 to 15% by mass or 10 to 15% by mass. By way of example, it may be, but is not limited to, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%. The electrolyte salt is at least one selected from lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonyl imide, lithium bisoxalato borate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorobisoxalato phosphate and lithium bisfluorosulfonyl imide. As an example, the lithium salt is lithium hexafluorophosphate (LiPF 6 ) Or lithium bisoxalato borate (LiBOB). In a preferred embodiment, the lithium salt is a mixture of two or more compounds, e.g., lithium hexafluorophosphate (LiPF 6 ) And lithium bis (oxalato) borate (LiBOB)The mixture, or the lithium salt is a mixture of lithium hexafluorophosphate and lithium trifluoromethane sulfonate, can obtain better and excellent high-temperature cycle performance.
Preferably, the nonaqueous organic solvent is at least one of a chain carbonate, a cyclic carbonate and a carboxylic acid ester. Further, 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). In some embodiments, the mass ratio of the nonaqueous organic solvent in the nonaqueous electrolytic solution is 65-90%, preferably 70-88%, more preferably 80-88%. As an example, the mass percentage of the nonaqueous organic solvent in the nonaqueous electrolytic solution may be, but is not limited to, 80%, 82%, 85%, 86%, 87%, 88%.
The second aspect of the invention provides a lithium ion battery, which comprises a positive electrode material, a negative electrode material, a separation membrane and lithium ion electrolyte, wherein the lithium ion electrolyte is the electrolyte.
Preferably, the highest charging voltage may be 4.535V. The positive electrode material includes at least one of a lithium cobalt oxide-based material, a lithium nickel cobalt manganese oxide-based material, and a lithium nickel cobalt aluminate-based material. Wherein the chemical formula of the lithium cobaltate material is LiCo 1-a M` a O 2 . M' is at least one selected from Mg, cu, zn, al, sn, B, ga, cr, sr, V and Ti, and a is more than or equal to 0 and less than or equal to 0.2. The chemical formula of the nickel cobalt lithium manganate material is LiNi x Co y Mn z M (1-x-y-z) O2, the chemical formula of the nickel cobalt aluminum oxide is LiNi x Co y Al z N (1-x-y-z) O2, wherein M, N are each independently selected from at least one of Mg, cu, zn, al, sn, B, ga, cr, sr, V and Ti, 0<x<1，0<y<1，0<z<1, x+y+z is less than or equal to 1. The positive electrode material may further include a positive electrode additive in addition to the positive electrode active material described above, and the positive electrode additive may be Lithium Lanthanum Zirconium Oxide (LLZO).
Preferably, 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. The carbon-based negative electrode material may be artificial graphite, natural graphite, hard carbon, or soft carbon. The titanium-based oxide negative electrode material may be lithium titanate. The silicon-based anode material may be a Si material, a silicon oxygen material, or a silicon carbon material.
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
In a glove box filled with argon (O) 2 ＜1ppm，H 2 O < 1 ppm), mixing Ethylene Carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) according to the weight ratio of EC:DEC=1:1:1 to obtain 86.5g of nonaqueous organic solvent, then adding 1.0g of compound 1 as an additive, dissolving and fully stirring, adding 12.5g of lithium hexafluorophosphate, and uniformly mixing to obtain the nonaqueous electrolyte.
(2) Preparation of the positive electrode
LiCoO is added with 2 Uniformly mixing the adhesive PVDF and the conductive agent SuperP according to the mass ratio of 95:1:4 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 negative electrode
The artificial graphite, the conductive agent SuperP, the thickener CMC and the adhesive SBR (styrene butadiene rubber emulsion) are prepared into slurry according to the mass ratio of 95:1.5:1.0:2.5, and the slurry is uniformly mixed, coated on two sides of a copper foil, and then dried and rolled to obtain the negative electrode plate.
(4) Preparation of lithium ion batteries
And (3) preparing the positive electrode, the diaphragm and the negative electrode into a soft-package battery core in a winding mode, packaging by adopting a polymer aluminum plastic film, filling the prepared lithium ion battery nonaqueous electrolyte, and preparing the lithium ion battery with the capacity of 4000mAh through the working procedures of formation, capacity division and the like.
The electrolyte formulations of examples 1 to 14 and comparative examples 1 to 2 are shown in table 1, and the procedure for preparing the electrolytes and preparing the batteries of examples 2 to 14 and comparative examples 1 to 2 are the same as in example 1.
Example 15
The difference from example 1 is that LiCoO was used in the preparation of the positive electrode 2 The Lithium Lanthanum Zirconium Oxide (LLZO), binder PVDF and conductive agent SuperP were mixed in a mass ratio of 93:2:1:4, and other preparation methods and conditions were the same as in example 1, and the electrolyte formulation was shown in table 1.
The electrolyte formulations of examples 16 and 17 are shown in table 1, and the procedure for preparing the electrolyte and preparing the battery is the same as in example 15.
Table 1 electrolyte formulations for each of the examples and comparative examples
The lithium ion batteries manufactured in examples 1 to 17 and comparative examples 1 to 2 were subjected to a high temperature cycle test under the following specific test conditions, and the test results are shown in table 2.
High temperature cycle test: the lithium ion batteries prepared in examples 1 to 17 and comparative examples 1 to 2 were placed in an incubator at 45℃respectively, and allowed to stand for 30 minutes to allow the lithium ion batteries to reach constant temperature. The first-turn discharge capacity of the recording battery was C0, charged with a constant current of 1C to a voltage of 4.535V, then charged with a constant voltage of 4.535V to a current of 0.05C, and then discharged with a constant current of 1C to a voltage of 3.0V. This is a charge-discharge cycle. Then, 1C/1C charge and discharge was performed at 45℃for 300 weeks, the discharge capacity was recorded as C1, and the capacity retention rate of the lithium ion battery was calculated using the following formula.
Capacity retention = (C1/C0) ×100%
Table 2 results of high temperature performance test of each of examples and comparative examples
| Group of | Capacity retention (%) |
| Example 1 | 83％ |
| Example 2 | 86％ |
| Example 3 | 88％ |
| Example 4 | 83％ |
| Example 5 | 83％ |
| Example 6 | 82％ |
| Example 7 | 91％ |
| Example 8 | 80％ |
| Example 9 | 86％ |
| Example 10 | 72％ |
| Example 11 | 78％ |
| Example 12 | 91％ |
| Example 13 | 84％ |
| Example 14 | 82％ |
| Example 15 | 85％ |
| Example 16 | 86％ |
| Example 17 | 85％ |
| Comparative example 1 | 58％ |
| Comparative example 2 | 66％ |
From the results of table 2, it is understood that the compounds a employed in examples 1 to 17 of the present invention have higher high-temperature cycle performance at 4.535V based on comparative examples 1 to 2, because the compound a has a halogen-substituted disulfonate group, which has higher oxidation stability, and can stably operate in a high-voltage (e.g., 4.5V) lithium ion battery. In addition, the sulfur atoms and substituent atoms are broken, so that a stable and uniform solid electrolyte interface film can be formed on the positive electrode, and the impedance of the lithium ion battery is reduced. Meanwhile, the halogenated groups can form a stable and low-impedance solid electrolyte interface film on the negative electrode so as to further reduce the impedance of the lithium ion battery and improve the cycle performance of the lithium ion battery.
As is clear from comparative examples 1, 3 to 10, when the haloalkyl group is fluoro-substituted, the high temperature cycle property is better, which is probably due to the fact that fluoro-substituted group has lower Li than chloro-alkyl group + Solvating power, which is weak, can increase the anion content in the solvating sheath, thereby enhancing Li + And the interaction capability with anions to improve the cycle performance of the lithium ion battery.
As can be seen from comparative examples 1, 3 to 9 and 11, R 1 And R is 3 The cycling performance of lithium ion batteries is better when the same substituents are present, which may be due to the symmetry of the substituents.
As can be seen from comparative examples 1, 6 and 12, R of Compound A 2 The substituent is the combination of linear perfluoroalkyl and cyclic perfluoroalkyl, so that the cycle performance of the lithium ion battery can be improved.
As can be seen from comparative examples 1, 4 to 5 and examples 15 to 17, the addition of LLZO to the positive electrode material makes the cycle performance of the lithium ion battery better, because LLZO as a lithium source can supplement the active lithium lost in the cycle of the lithium ion battery, and the addition of compound a to the electrolyte can further enhance the cycle performance of the lithium ion battery.
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 comprising an electrolyte salt, a non-aqueous organic solvent and an additive, characterized in that the additive comprises a compound A shown in the structural formula 1,
wherein R is 1 And R is 3 Each independently selected from halogen or C 1 ～C 3 Haloalkyl radicals R of (2) 2 Selected from C 1 ～C 6 A haloalkyl or carbonyl-containing group of (a).
2. The nonaqueous electrolytic solution according to claim 1, wherein R 11 And R is 3 Each independently selected from fluorine or C 1 ～C 3 R is fluoroalkyl of (2) 2 Selected from C 1 ～C 6 Fluorinated alkyl, C 5 ～C 6 A fluorinated cycloalkyl group or a fluorinated alkanonyl group.
3. The nonaqueous electrolytic solution according to claim 1, wherein the mass ratio of the compound a is 0.05 to 5.0% based on 100% of the sum of the mass of the electrolyte salt, the nonaqueous organic solvent and the additive.
4. The nonaqueous electrolyte according to claim 1, wherein the compound A is at least one selected from the group consisting of compound 1 to compound 9,
5. the nonaqueous electrolytic solution according to claim 1, wherein the mass ratio of the electrolyte salt is 5 to 20% based on 100% of the sum of the mass of the electrolyte salt, the nonaqueous organic solvent 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 bisoxalato borate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorobisoxalato phosphate and lithium bisfluorosulfonyl imide.
7. The nonaqueous electrolyte according to claim 1, wherein the nonaqueous organic solvent is at least one of a chain carbonate, a cyclic carbonate and a carboxylic acid ester.
8. The nonaqueous electrolyte according to claim 7, wherein the nonaqueous organic solvent is at least one selected from the group consisting of ethylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, propylene carbonate, butyl acetate, γ -butyrolactone, propyl propionate, ethyl propionate and ethyl butyrate.
9. A lithium ion battery comprising a positive electrode material, a negative electrode material and a lithium ion electrolyte, wherein the lithium ion electrolyte is the nonaqueous electrolyte according to any one of claims 1 to 8.
10. The lithium ion battery of claim 9, wherein the positive electrode material comprises at least one of a lithium cobalt oxide-based material, a lithium nickel cobalt manganese oxide-based material, and a lithium nickel cobalt aluminate-based material.
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