CN116053590A - Lithium ion battery electrolyte, lithium ion battery and electric equipment - Google Patents
Lithium ion battery electrolyte, lithium ion battery and electric equipment Download PDFInfo
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- CN116053590A CN116053590A CN202310310683.XA CN202310310683A CN116053590A CN 116053590 A CN116053590 A CN 116053590A CN 202310310683 A CN202310310683 A CN 202310310683A CN 116053590 A CN116053590 A CN 116053590A
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- ion battery
- lithium ion
- group
- lithium
- battery electrolyte
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 111
- 239000003792 electrolyte Substances 0.000 title claims abstract description 80
- -1 bipyridine disulfide derivative Chemical class 0.000 claims abstract description 51
- 239000000654 additive Substances 0.000 claims abstract description 40
- 230000000996 additive effect Effects 0.000 claims abstract description 38
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 26
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 9
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 claims description 6
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 claims description 6
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 6
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 claims description 6
- 150000002596 lactones Chemical class 0.000 claims description 6
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 6
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- 229920001774 Perfluoroether Polymers 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 claims description 3
- VIHAEDVKXSOUAT-UHFFFAOYSA-N but-2-en-4-olide Chemical compound O=C1OCC=C1 VIHAEDVKXSOUAT-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229940125904 compound 1 Drugs 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 21
- 239000002000 Electrolyte additive Substances 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 239000006183 anode active material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000006978 adaptation Effects 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- BWUZCLFBFFQLLM-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-yl hydrogen carbonate Chemical compound FC(F)(F)C(C)OC(O)=O BWUZCLFBFFQLLM-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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 application provides lithium ion battery electrolyte, a lithium ion battery and electric equipment, and belongs to the field of lithium ion battery manufacturing. Comprises an organic solvent, lithium salt and an additive, wherein the additive comprises bipyridine disulfide derivative with a structural general formula shown in a formula I: wherein R1-R8 are independently selected from one of fluorine atom, cyano, C1-C6 alkyl and C1-C6 fluorine-containing alkyl, and the lithium ion battery electrolyte can improve the high-low temperature performance of the lithium ion battery in high-voltage environment to a certain extent.
Description
Technical Field
The application relates to the field of lithium ion battery manufacturing, in particular to lithium ion battery electrolyte, a lithium ion battery and electric equipment.
Background
In the prior art, the lithium ion battery is widely applied because of the advantages of high energy density, good cycle performance and the like, along with the increase of the requirements of the new energy automobile on the endurance mileage, the application voltage of the lithium ion battery is gradually increased (generally 4.5V and above), the general application voltage environment of the existing type of electrolyte additives (such as 1, 3-propylene sultone and maleic anhydride) is below 4.4V, and the problem of poor high-low temperature performance of the corresponding lithium ion battery exists when the lithium ion battery is applied in a high-voltage environment.
Disclosure of Invention
The purpose of this application is to provide a lithium ion battery electrolyte, lithium ion battery and consumer, can improve the high low temperature performance when lithium ion battery uses under high voltage environment to a certain extent.
Embodiments of the present application are implemented as follows:
in a first aspect, embodiments of the present application provide a lithium ion battery electrolyte, including an organic solvent, a lithium salt, and an additive, the additive including a bipyridine disulfide derivative having a structural formula as shown in formula I:
i is a kind of
Wherein R is 1 ~R 8 Are independently selected from one of fluorine atom, cyano, C1-C6 alkyl and C1-C6 fluorine-containing alkyl.
In the technical scheme, the additive component with the structural general formula in the lithium ion battery electrolyte can form a stable and thinner CEI film on the surface of the positive electrode when the disulfide bond in the bipyridine disulfide derivative and a plurality of functional groups introduced on the pyridine ring are applied in a high-voltage environment, and the film can passivate the interface of the positive electrode, reduce the oxidative decomposition of the electrolyte at the positive electrode of the battery and inhibit the increase of the interface impedance of the battery, so that the low-temperature performance (such as low-temperature discharge retention rate) of the battery when the battery is applied at high voltage is improved; on the other hand, the pyridine ring in the bipyridine disulfide derivative has stronger coordination capability, and can complex metal ions (such as Ni 2+ And Mn of 2+ ) To reduce the risk of metal ions accumulating at and damaging the battery anode, thereby improving the high temperature performance (e.g., high temperature cycling performance) of the battery when applied at high voltages. Bipyramid is prepared by the synergistic effect of two aspectsThe pyridine disulfide derivative is used as an additive of the electrolyte, so that the high-low temperature performance of the lithium ion battery in the high-voltage environment can be improved to a certain extent.
In some alternative embodiments, each of R1-R8 is independently selected from one of fluorine atom, cyano, methyl, ethyl, propyl, phenyl, vinyl, propenyl, ethynyl, propynyl, fluoromethyl, fluoroethyl, fluoropropyl, fluorovinyl, fluoropropenyl, fluorobutenyl, and fluorophenyl.
In the technical scheme, R1-R8 are limited in the range, and compared with other structures, the battery has better high-low temperature performance when being applied under high voltage.
In some alternative embodiments, R1-R8 are each independently selected from one of fluorine atom, cyano, methyl, ethenyl, propenyl, ethynyl, propynyl, fluoromethyl, fluoroethyl, fluoropropyl, fluorovinyl, fluoropropenyl, fluorobutenyl, and fluorophenyl.
In the technical scheme, R1-R8 are further limited in a more preferable range, and compared with other structures, the high-low temperature performance of the battery can be further improved when the battery is applied under high voltage.
In some alternative embodiments, the mass percent of bipyridine disulfide derivative in the lithium ion battery electrolyte is 0.1-3%.
In the above technical scheme, the amount of bipyridine disulfide derivative is limited to the above range, because: if the consumption of the bipyridine disulfide derivative is too low, the high-low temperature performance of the corresponding battery cannot be effectively improved; if the amount of the bipyridine disulfide derivative is too high, an excessively thick CEI film is formed, so that the battery is excessively polarized, and the high-low temperature performance of the battery is difficult to effectively improve.
In some alternative embodiments, the additive further comprises one or more of vinyl sulfate, fluoroethylene carbonate, 1, 3-propenolactone, ethylene carbonate, 1, 3-propane sultone, methylene methylsulfonate, allyl isocyanate, triallyl isocyanurate, 2 (5H) -furanone, 2-methyl maleic anhydride, tris (trimethylsilyl) phosphite, and tripropenyl phosphate.
In the technical scheme, the additive also contains the components, so that more functions can be given to the electrolyte, and the comprehensive electrical properties (such as safety performance, high-low temperature performance and the like) of the corresponding battery are more comprehensively improved.
In some alternative embodiments, the additive further comprises one or more of fluoroethylene carbonate, 1, 3-propenesulfonic acid lactone, ethylene carbonate, 1, 3-propane sultone, methylene methylsulfonate.
In the above technical solution, the components of the additional additive are further limited in a more preferable range, and the functional components are more easily adapted, so that the comprehensive electrical performance of the corresponding battery can be further improved.
In some alternative embodiments, the mass percentage of the additive in the lithium ion battery electrolyte is 0.1-20%.
In the technical scheme, the dosage of the additive is limited in the range, so that the additive has proper dosage, and the comprehensive electrical property of the battery can be better improved.
In some alternative embodiments, the organic solvent comprises one or more of ethylene carbonate, propylene carbonate, methylethyl carbonate, dimethyl carbonate, carbonates, carboxylates, fluoroethers, propylene 3, 3-trifluorocarbonate, methyltrifluoroethyl carbonate, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether fluorocarbonate, fluorocarboxylates, and dimethyl fluorocarbonate.
The scheme of the application can be better suitable for various organic solvent systems, and more implementable modes are provided, so that popularization and application are facilitated.
In some of the alternative embodiments of the present invention, the organic solvent comprises propylene carbonate, 3-trifluoro propylene carbonate, methyl trifluoro ethyl carbonate 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether fluorocarbonate, fluorocarboxylate, and fluorodimethyl carbonate.
In the above technical scheme, the types of the organic solvents are further limited in a more preferable range, and the comprehensive electrical properties of the corresponding battery can be better improved due to easier adaptation among the functional components.
In some alternative embodiments, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorosulfonimide, lithium difluorobisoxalato phosphate, lithium tetrafluorooxalato phosphate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl) imide, and lithium bisoxalato borate.
The scheme of the application can be better suitable for various lithium salt systems, and more implementable modes are provided, so that popularization and application are facilitated.
In some alternative embodiments, the lithium salt comprises one or more of the lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorobis oxalato phosphate, and lithium difluorooxalato borate.
In the above technical scheme, the types of lithium salts are further limited in a more preferable range, and the comprehensive electrical properties of the corresponding battery can be better improved due to easier adaptation among the functional components.
In some alternative embodiments, the mass percentage of lithium salt in the lithium ion battery electrolyte is 10-20%.
In the technical scheme, the dosage of the additive is limited in the range, so that the lithium salt has proper dosage, and the comprehensive electrical property of the battery can be better improved.
In a second aspect, embodiments of the present application provide a lithium ion battery comprising a housing, an electrode assembly, and a lithium ion battery electrolyte as provided in the embodiments of the first aspect. The electrode assembly is accommodated in the case; the lithium ion battery electrolyte is contained in the shell.
In the above technical solution, the lithium ion battery includes the battery electrolyte provided in the embodiment of the first aspect, and in a high voltage application environment of 4.5V and above, a stable and thinner CEI film can be formed on the surface of the positive electrode, and the film can passivate the interface of the positive electrode, reduce the oxidative decomposition of the electrolyte in the positive electrode of the battery, and inhibit the interface resistance of the batteryResistance to increase, and at the same time, can complex metal ions (e.g., li + And Mn of 2+ ) The method reduces the risk that metal ions accumulate in the battery cathode and damage the battery cathode, thereby improving the high-low temperature performance of the lithium ion battery in a high-voltage environment to a certain extent.
In some alternative embodiments, the battery positive electrode of the electrode assembly satisfies at least one of the following conditions (a) and (b):
(a) The positive electrode active material includes LiNi x Co y Mn z O 2 Wherein x+y+z=1, 0 < x < 1,0 < y < 1,0 < z < 1;
(b) The positive electrode active material includes LiNi 0.5 Mn 1.5 O 4 。
The scheme of the application can be well applied to the multiple positive electrode active material systems, and more implementable modes are provided, so that popularization and application are facilitated; in addition, it is also noted that the use of the above-described type of positive electrode active material also has the advantage of being more resistant to high voltages than the use of other types of positive electrode active materials.
In some alternative embodiments, the negative electrode active material in the battery negative electrode of the electrode assembly includes one or more of graphite, graphite composite, and silicon oxide.
The scheme of the application can be well applied to the multiple anode active material systems, and more implementable modes are provided, so that popularization and application are facilitated.
In some alternative embodiments, the negative electrode active material includes one or more of graphite and a graphite composite.
In the above technical scheme, the types of the anode active materials are further limited in a more preferable range, and the comprehensive electrical properties of the corresponding battery can be better improved due to easier adaptation among the functional components.
In a third aspect, embodiments of the present application provide an electrical device, where the electrical device includes a lithium ion battery as provided in the embodiments of the second aspect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In this application, "and/or" such as "feature 1 and/or feature 2" means that "feature 1" alone, and "feature 2" alone, and "feature 1" plus "feature 2" alone, are all possible.
In addition, in the description of the present application, unless otherwise indicated, "one or more" means "a plurality of" means two or more; the range of the values a to b includes the two end values "a" and "b", and the "measurement unit" in the values a to b+measurement unit "represents the" measurement unit "of both the values a and b.
In the prior art, current electrolyte additives (e.g., 1, 3-propenolactone and maleic anhydride) generally suffer from the following problems:
the film forming potential of the electrolyte additive A is low, and the electrolyte additive generally participates in film forming below 4.4 and V, and accordingly, the residual quantity at a higher voltage is low, so that the film cannot be formed effectively, and the high-low temperature performance of the battery is poor.
The film forming resistance of the electrolyte additive B is high, so that the low-temperature performance of the corresponding battery is poor.
The problem that metal ions precipitated from the positive electrode of the battery accumulate in the negative electrode of the battery and damage the negative electrode of the battery easily cannot be effectively solved by the additive of the electrolyte C, so that the corresponding battery has poor high-temperature performance.
Based on this, the inventors studied to find that: the bipyridine disulfide derivative is used as an electrolyte additive, and the disulfide bond, the pyridine ring and various substituent functional groups of the bipyridine disulfide derivative can improve the high-low temperature performance of the lithium ion battery in a high-voltage environment to a certain extent.
The embodiment of the application is specifically described below for lithium ion battery electrolyte, lithium ion battery and electric equipment.
In a first aspect, embodiments of the present application provide a lithium ion battery electrolyte, including an organic solvent, a lithium salt, and an additive, the additive including a bipyridine disulfide derivative having a structural formula as shown in formula I:
i is a kind of
Wherein R is 1 ~R 8 Are independently selected from one of fluorine atom, cyano, C1-C6 alkyl and C1-C6 fluorine-containing alkyl.
In the application, the additive component with the structural general formula in the lithium ion battery electrolyte, on one hand, when disulfide bonds in bipyridine disulfide derivatives and a plurality of functional groups introduced on pyridine rings are applied in a high-voltage environment, a stable and thinner CEI film can be formed on the surface of a positive electrode, and the film can passivate the interface of the positive electrode, reduce the oxidative decomposition of the electrolyte at the positive electrode of the battery and inhibit the increase of the interface impedance of the battery, so that the low-temperature performance (such as low-temperature discharge retention rate) of the battery when the battery is applied at high voltage is improved; on the other hand, the pyridine ring in the bipyridine disulfide derivative has stronger coordination capability, and can complex metal ions (such as Ni 2+ And Mn of 2+ ) To reduce the risk of metal ions accumulating at and damaging the battery anode, thereby improving the high temperature performance (e.g., high temperature cycling performance) of the battery when applied at high voltages. Through the synergistic effect of the two aspects, the bipyridine disulfide derivative is used as an additive of the electrolyte, so that the high-low temperature performance of the lithium ion battery in the application under the high-voltage environment can be improved to a certain extent.
The high-low temperature performance includes various specific parameters including the cycle performance at high temperature and the discharge retention rate at low temperature, and at least the cycle performance at high temperature and the discharge retention rate at low temperature in the high-low temperature performance can be improved in the present application.
As an example, R1 to R8 are each independently selected from one of fluorine atom, cyano group, methyl group, ethyl group, propyl group, phenyl group, vinyl group, propenyl group, ethynyl group, propynyl group, fluoromethyl group, fluoroethyl group, fluoropropyl group, fluorovinyl group, fluoropropenyl group, fluorobutenyl group, and fluorophenyl group.
In this embodiment, R1 to R8 are limited to the above range, so that the battery has better high-low temperature performance when applied under high voltage, compared with other structures.
It can be understood that the variety of substituents can be further adjusted in order to better improve the high-low temperature performance of the lithium ion battery when the lithium ion battery is applied in a high-voltage environment due to the difference of physical and chemical properties.
As an example, R1 to R8 are each independently selected from one of fluorine atom, cyano group, methyl group, vinyl group, propenyl group, ethynyl group, propynyl group, fluoromethyl group, fluoroethyl group, fluoropropyl group, fluorovinyl group, fluoropropenyl group, fluorobutenyl group, and fluorophenyl group.
In the embodiment, R1 to R8 are further limited in a more preferable range, and compared with other structures, the high-low temperature performance of the battery can be further improved when the battery is applied under high voltage.
As one example, bipyridine disulfide derivatives include one or more of the following compounds:
compound 1
Compound 2
Compound 3
Compound 4
Compound 5
Compound 6
It is understood that the mass percentage of the bipyridine disulfide derivative in the electrolyte is related to the performance improvement degree of the corresponding battery, and the mass percentage of the bipyridine disulfide derivative in the electrolyte can be adjusted in consideration of the improvement effect of the bipyridine disulfide derivative on the high and low temperature performance of the battery when the battery is applied under high voltage.
As an example, the mass percent of bipyridine disulfide derivative in the lithium ion battery electrolyte is 0.1-3%, such as, but not limited to, any one point value or a range value between any two of 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5% and 3%.
In this embodiment, the amount of the bipyridine disulfide derivative is limited to the above range, because: if the consumption of the bipyridine disulfide derivative is too low, the high-low temperature performance of the corresponding battery cannot be effectively improved; if the amount of the bipyridine disulfide derivative is too high, an excessively thick CEI film is formed, so that the battery is excessively polarized, and the high-low temperature performance of the battery is difficult to effectively improve.
It will be appreciated that in order to better enhance the overall electrical performance of the battery, the electrolyte typically does not contain only one additive.
As one example, the additive further includes one or more of vinyl sulfate, fluoroethylene carbonate, 1, 3-propenesulfonic acid lactone, ethylene carbonate, 1, 3-propane sultone, methylene methyldisulfonate, allyl isocyanate, triallyl isocyanurate, 2 (5H) -furanone, 2-methyl maleic anhydride, tris (trimethylsilyl) phosphite, and tripropenyl phosphate.
In this embodiment, the additive further contains the above components, so that more functions can be given to the electrolyte, and thus the overall electrical properties (such as safety performance and high-low temperature performance) of the corresponding battery can be more comprehensively improved.
It can be understood that the variety of auxiliary additives can be further adjusted in order to better improve the high-low temperature performance of the lithium ion battery when the lithium ion battery is applied in a high-voltage environment due to the difference of physical and chemical properties.
As one example, the additive further includes one or more of fluoroethylene carbonate, 1, 3-propenesulfonic acid lactone, ethylene carbonate, 1, 3-propane sultone, and methylene methylsulfonate.
In this embodiment, the components of the additional additives are further limited to a more preferable range, and thus the overall electrical properties of the corresponding battery can be further improved due to easier adaptation between the respective functional components.
It can be appreciated that the mass percentage of the additive in the electrolyte can affect the overall electrical performance of the battery, and in order to better improve the overall electrical performance of the battery, the mass percentage of the additive in the electrolyte of the lithium ion battery can be adjusted.
As an example, the mass percent of the additive in the lithium ion battery electrolyte is 0.1-20%, such as, but not limited to, any one point value or a range value between any two of 0.1%, 0.5%, 1%, 5%, 10%, 15% and 20%.
In this embodiment, the amount of the additive is limited to the above range, so that the additive can be appropriately used, thereby improving the overall electrical properties of the battery.
As an example of this, in one embodiment, the organic solvent comprises ethylene carbonate, propylene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbonic ester, carboxylic ester, fluoroether, 3-trifluoro propylene carbonate methyl trifluoroethyl carbonate, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether fluorocarbonate, fluorocarboxylate, and fluorodimethyl carbonate.
In the embodiment, the scheme of the application can be better suitable for various organic solvent systems, and more embodiments are provided, so that popularization and application are facilitated.
It can be understood that the variety of organic solvents can be further adjusted in order to better improve the high-low temperature performance of the lithium ion battery when the lithium ion battery is applied in a high-voltage environment due to the difference of physical and chemical properties.
As an example of this, in one embodiment, the organic solvent comprises propylene carbonate, 3-trifluoro propylene carbonate, methyl trifluoro ethyl carbonate 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether fluorocarbonate, fluorocarboxylate, and fluorodimethyl carbonate.
In this embodiment, the kind of the organic solvent is further limited to a more preferable range, and the overall electrical properties of the corresponding battery can be better improved due to easier adaptation between the respective functional components.
As one example, the lithium salt includes one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorosulfonimide, lithium difluorobisoxalato phosphate, lithium tetrafluorooxalato phosphate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl) imide, and lithium bisoxalato borate.
In the embodiment, the scheme of the application can be better suitable for various lithium salt systems, and more embodiments are provided, so that popularization and application are facilitated.
It is understood that various lithium salts have differences in physical and chemical properties, and the types of lithium salts can be further adjusted in order to better improve the high and low temperature performance of the lithium ion battery when the lithium ion battery is applied in a high voltage environment.
As one example, the lithium salt includes one or more of the lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorobis oxalato phosphate, and lithium difluorooxalato borate.
In this embodiment, the kind of lithium salt is further limited to a more preferable range, and the overall electrical properties of the corresponding battery can be better improved due to easier adaptation between the respective functional components.
As an example, the mass percentage of lithium salt in the lithium ion battery electrolyte is 10-20%.
In this embodiment, the amount of the additive is limited to the above range, so that the lithium salt can be appropriately used, thereby improving the overall electrical properties of the battery.
In the embodiment, the scheme of the application can be better suitable for various lithium salt systems, and more embodiments are provided, so that popularization and application are facilitated.
Further, the types of lithium salts are limited in a specific range, and the functional components are more easily matched, so that the comprehensive electrical performance of the corresponding battery can be better improved.
Further, the amount of the additive is limited to the above range, so that the lithium salt can be appropriately used, thereby improving the overall electrical properties of the battery.
The functional components of the lithium ion battery electrolyte, which are not specifically described or defined, are not particularly limited, and may be selected and set according to conventional methods in the art.
In a second aspect, embodiments of the present application provide a lithium ion battery comprising a housing, an electrode assembly, and a lithium ion battery electrolyte as provided in the embodiments of the first aspect. The electrode assembly is accommodated in the case; the lithium ion battery electrolyte is contained in the shell.
In this embodiment, the lithium ion battery includes the battery electrolyte provided in the example of the first aspect, and in the high voltage application environment of 4.5V and above, a stable and thin CEI film can be formed on the surface of the positive electrode, which can passivate the positive electrode interface, reduce the oxidative decomposition of the electrolyte at the positive electrode of the battery, and suppress the increase of the interface impedance of the battery, and at the same time, can complex the metal ions (such as Li + And Mn of 2+ ) To reduce the accumulation of metal ions in the negative electrode of the batteryThe risk of damaging the negative electrode of the battery is improved to a certain extent, so that the high-low temperature performance of the lithium ion battery in the application under the high-voltage environment can be improved.
In the electrode assembly, the type of the positive electrode active material is not limited, and may be set according to conventional choices in the art.
As one example, the battery positive electrode of the electrode assembly satisfies at least one of the following conditions (a) and (b):
(a) The positive electrode active material includes LiNi x Co y Mn z O 2 Wherein x+y+z=1, 0 < x < 1,0 < y < 1,0 < z < 1.
(b) The positive electrode active material includes LiNi 0.5 Mn 1.5 O 4 。
In the embodiment, the scheme of the application can be better suitable for various positive electrode active material systems, and more embodiments are provided, so that popularization and application are facilitated; in addition, it is also noted that the use of the above-described type of positive electrode active material also has the advantage of being more resistant to high voltages than the use of other types of positive electrode active materials.
In the electrode assembly, the type of the battery anode active material is not limited, and may be set according to conventional choices in the art.
As one example, in a battery anode of an electrode assembly, an anode active material includes one or more of graphite, a graphite composite material, and silicon oxide.
In the embodiment, the scheme of the application can be better suitable for various anode active material systems, and more embodiments are provided, so that popularization and application are facilitated.
It can be understood that the variety of the anode active materials can be further adjusted in order to better improve the high-low temperature performance of the lithium ion battery when the lithium ion battery is applied in a high-voltage environment due to the difference of physical and chemical properties.
As one example, the negative active material includes one or more of graphite and a graphite composite material.
In this embodiment, the kind of the anode active material is further limited to a more preferable range, and since the respective functional components are more easily adapted, the overall electrical properties of the corresponding battery can be better improved.
The structure or functional unit of the lithium ion battery, which is not specifically described or defined, is not particularly limited, and may be selected and set according to conventional methods in the art.
In a third aspect, embodiments of the present application provide an electrical device, where the electrical device includes a lithium ion battery as provided in the embodiments of the second aspect.
It should be noted that the type of the electric equipment is not limited, and is, for example, a mobile phone, a portable device, a notebook computer, a battery car, an electric automobile, a ship, a spacecraft, an electric toy, an energy storage device, an electric tool, and the like.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which comprises the following steps:
ethylene Carbonate (EC), dimethyl Fluorocarbonate (FDMC) and methyl trifluoroethyl carbonate (FEMC) are mixed according to a mass ratio of 2:5:3, mixing to obtain a mixed organic solvent; then, lithium hexafluorophosphate (LiPF) was added to the mixed organic solvent 6 ) And the compound 1 are uniformly mixed to obtain lithium ion battery electrolyte; wherein, according to mass percent, mixing organic solvent: lithium hexafluorophosphate: compound 1=89.9: 10:0.1.
example 2
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 1 in that: mixing organic solvents according to mass percent: lithium hexafluorophosphate: compound 1=84: 15:1.
example 3
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 1 in that: mixing organic solvents according to mass percent: lithium hexafluorophosphate: compound 1=77: 20:3.
example 4
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: 1% of compound 1 was replaced with 1% of compound 2.
Example 5
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: 1% of compound 1 was replaced with 1% of compound 3.
Example 6
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: 1% of compound 1 was replaced with 1% of compound 4.
Example 7
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: 1% of compound 1 was replaced with 1% of compound 5.
Example 8
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: 1% of compound 1 was replaced with 1% of compound 6.
Example 9
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: 1% of compound 1 was replaced with 0.5% of compound 1 and 0.5% of compound 2.
Example 10
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: 1% of compound 1 was replaced with 0.5% of compound 1, 0.25% of compound 2 and 0.25% of compound 3.
Example 11
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: the mass percentage of the compound 1 was 0.05%, and the change in the amount was adjusted by mixing the amounts of the organic solvents.
Example 12
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: the mass percentage of the compound 1 was 0.1%, and the change in the amount was adjusted by mixing the amounts of the organic solvents.
Example 13
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: the mass percentage of the compound 1 was 3%, and the amount was adjusted by mixing the amounts of the organic solvents.
Example 14
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: the mass percentage of the compound 1 was 5%, and the amount was adjusted by mixing the amounts of the organic solvents.
Example 15
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: adding lithium hexafluorophosphate (LiPF) to the mixed organic solvent 6 ) The compound 1 and 2% fluoroethylene carbonate (FEC) are uniformly mixed to obtain the lithium ion battery electrolyte, and the change of the dosage is adjusted by the dosage of the mixed organic solvent.
Example 16
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: adding lithium hexafluorophosphate (LiPF) to the mixed organic solvent 6 ) And uniformly mixing the compound 1 and 2% of 2-methyl maleic anhydride (DMMA) to obtain the lithium ion battery electrolyte, wherein the change of the dosage is adjusted by mixing the dosage of the organic solvent.
Example 17
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: 10% lithium hexafluorophosphate (LiPF) 6 ) Replacement with 10% lithium hexafluorophosphate (LiPF) 6 ) 5% ofLithium bis (fluorosulfonyl) imide (LiFSI).
Example 18
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: the fluorodimethyl carbonate (FDMC) was replaced entirely with methylethyl carbonate (EMC).
Example 19
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: replacement of compound 1 entirely with compound 7 (wherein two CFs were replaced 3 Respectively ethyl).
Example 20
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: replacement of compound 1 entirely with compound 8 (wherein two CFs were replaced 3 Respectively substituted by propyl).
Comparative example 1
The embodiment of the application provides a preparation method of lithium ion battery electrolyte, which only differs from embodiment 2 in that: all of compound 1 was replaced with 1, 3-propenesulfonic acid lactone (PST).
For ease of understanding, a centralized arrangement is performed by table 1 below.
The amount of the organic solvent used was the balance excluding the contents shown in table 1 below.
Table 1 component tables of examples and comparative examples
Test example 1
Electrical property test
The testing method comprises the following steps:
the lithium ion battery electrolytes prepared in examples 1 to 20 and comparative example 1 were assembled into batteries and numbered correspondingly, and then the batteries were tested for capacity retention rate of 100 cycles at 25 c, capacity retention rate of 100 cycles at 45 c, and discharge retention rate at-20 c, respectively.
Wherein, the liquid crystal display device comprises a liquid crystal display device,
the battery is assembled as follows:
s1, according to 96:2:2 mass ratio of LiNi 0.5 Mn 1.5 O 4 (positive electrode active material), conductive carbon black (conductive agent) and polyvinylidene fluoride (binder) dispersed in N-methyl-2-pyrrolidone to obtain a positive electrode slurry; then, uniformly coating the positive electrode slurry on two sides of the aluminum foil; then, the positive plate with the thickness of 125 μm is obtained after the aluminum outgoing line is welded by an ultrasonic welder through drying, calendaring and vacuum drying in sequence.
S2, according to the proportion of 95:1.5:1.5: mixing graphite (anode active material), conductive carbon black (conductive agent), styrene-butadiene rubber and carboxymethyl cellulose (binder) according to the mass ratio of 2, and dispersing the mixture in deionized water to obtain anode slurry; then, coating the negative electrode slurry on two sides of the copper foil; then, the negative electrode sheet with the thickness of 125 μm is obtained after the nickel lead-out wire is welded by an ultrasonic welder through drying, calendaring and vacuum drying in sequence.
S3, winding the prepared positive plate, negative plate and ion diaphragm (PP/PE/PP three-layer composite diaphragm) to obtain a bare cell, then injecting the bare cell, the shell and the high-voltage electrolyte groups prepared in examples 1-12 and comparative examples 1-5 into a dried battery, and packaging, standing, forming, shaping and capacity testing to complete the battery.
The test of the corresponding electrical parameters of the battery and the corresponding calculation formula are as follows:
capacity retention test of the cell for 100 cycles at 25 ℃): the battery was left at 25 ℃ and was cycled between charge and discharge using a current of 0.5C at a charge and discharge voltage interval of 3.5-4.85V, and the discharge holding capacity for the 100 th cycle was recorded.
Capacity retention test of the cell for 100 cycles at 45 ℃): the battery was left at 45 ℃ and was cycled between charge and discharge with a current of 0.5C at a charge and discharge voltage interval of 3.5-4.85V, and the discharge holding capacity for the 100 th cycle was recorded.
Low temperature discharge test at-20 ℃ for battery: the battery was charged and discharged 3 times at room temperature (25 ℃) with a current of 0.33C in a charge-discharge pressure interval of 3.5 to 4.85V, the last 1 discharge capacity was taken as the initial capacity at room temperature, then 0.33C was charged fully, the battery was left at low temperature (-20 ℃) for 4 hours, and then discharged to 3.0V at a constant current of 0.33C to obtain a low-temperature discharge capacity.
The calculation formula is as follows:
100-cycle capacity retention (%) = (100 th discharge retention capacity/1 st cycle discharge capacity) ×100%;
low-temperature discharge capacity retention (%) =low Wen Chushi discharge capacity/room temperature initial discharge capacity×100%.
Table 2 battery performance test results
Referring to table 2, as can be seen from the performance test results of example 2 and comparative example 1, the electrolyte additive provided in the examples of the present application has better high-low temperature performance than the conventional electrolyte additive.
As can be seen from the performance test results of examples 1 to 3, the electrolyte additive provided by the examples of the present application is adopted within the dosage range provided by the examples of the present application, and the corresponding lithium ion batteries have better high-low temperature performance.
As shown by the performance test results of the embodiment 2 and the embodiments 4 to 10, when the use amount of the electrolyte additive is fixed, the corresponding lithium ion battery has better high-low temperature performance by adopting one or more bipyridine disulfide derivatives provided by the embodiment of the application.
As can be seen from the performance test results of examples 2 and examples 11 to 14, the amount of the electrolyte additive is limited to the range of the amount provided in the examples of the present application, and the lithium ion battery corresponding to the above method has better high-low temperature performance than the lithium ion battery not in the set range.
As can be seen from the performance test results of examples 2 and 15-16, the addition of the auxiliary additive provided in the examples of the present application to the electrolyte additive can further improve the high-low temperature performance of the corresponding battery, and when the auxiliary additive is an auxiliary additive within a more preferable range, the improvement of the high-low temperature performance of the corresponding battery is more obvious.
As can be seen from the performance test results of example 2 and example 17, when all lithium salts are selected from the lithium salts within the more preferable ranges provided in the examples of the present application, the corresponding battery can have better high-low temperature performance.
From the performance test results of examples 2 and 18, it is understood that the organic solvents in the preferred ranges provided in the examples of the present application can provide the corresponding batteries with better high-low temperature performance.
From the performance test results of examples 2 and 19 to 20, it is understood that when the structural formula of the bipyridine disulfide derivative is limited to the more preferable range provided in the examples of the present application, the lithium ion battery corresponding to the former has better high-low temperature performance than the lithium ion battery not in the more preferable range.
The embodiments described above are some, but not all, of the embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Claims (17)
1. The lithium ion battery electrolyte is characterized by comprising an organic solvent, lithium salt and an additive, wherein the additive comprises a bipyridine disulfide derivative with a structural general formula shown in a formula I:
i is a kind of
Wherein R is 1 ~R 8 Are each independently selected from fluorine atom, cyano group, hydrocarbon group of C1 to C6 and fluorine-containing of C1 to C6One of the hydrocarbon groups.
2. The lithium ion battery electrolyte according to claim 1, wherein R1 to R8 are each independently selected from one of fluorine atom, cyano group, methyl group, ethyl group, propyl group, phenyl group, vinyl group, propenyl group, ethynyl group, propynyl group, fluoromethyl group, fluoroethyl group, fluoropropyl group, fluorovinyl group, fluoropropenyl group, fluorobutenyl group, and fluorophenyl group.
3. The lithium ion battery electrolyte according to claim 2, wherein R1 to R8 are each independently selected from one of the fluorine atom, the cyano group, the methyl group, the vinyl group, the propenyl group, the ethynyl group, the propynyl group, the fluoromethyl group, the fluoroethyl group, the fluoropropyl group, the fluorovinyl group, the fluoropropenyl group, the fluorobutenyl group, and the fluorophenyl group.
4. The lithium ion battery electrolyte according to claim 1, wherein the mass percentage of the bipyridine disulfide derivative in the lithium ion battery electrolyte is 0.1-3%.
5. The lithium ion battery electrolyte according to any one of claims 1 to 4, wherein the additive further comprises one or more of vinyl sulfate, fluoroethylene carbonate, 1, 3-propenesulfonic acid lactone, ethylene carbonate, 1, 3-propane sultone, methylene methyldisulfonate, allyl isocyanate, triallyl isocyanurate, 2 (5H) -furanone, 2-methyl maleic anhydride, tris (trisilane) phosphite, and tripropenyl phosphate.
6. The lithium ion battery electrolyte of claim 5, wherein the additive further comprises one or more of the fluoroethylene carbonate, the 1, 3-propenesulfonic acid lactone, the ethylene carbonate, the 1, 3-propane sultone, and the methylene methylsulfonate.
7. The lithium ion battery electrolyte according to claim 5, wherein the mass percentage of the additive in the lithium ion battery electrolyte is 0.1-20%.
8. The lithium ion battery electrolyte according to any one of claim 1 to 4, wherein, the organic solvent comprises ethylene carbonate, propylene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbonic ester, carboxylic ester, fluoroether, 3-trifluoro propylene carbonate methyl trifluoroethyl carbonate, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether fluorocarbonate, fluorocarboxylate, and fluorodimethyl carbonate.
9. The lithium ion battery electrolyte of claim 8, wherein the organic solvent comprises one or more of the propylene carbonate, the 3, 3-trifluoropropylene carbonate, the methyl trifluoroethyl carbonate, the 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether fluorocarbonate, the fluorocarboxylic acid ester, and the dimethyl fluorocarbonate.
10. The lithium ion battery electrolyte according to any one of claims 1 to 4, wherein the lithium salt comprises one or more of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorobisoxalato phosphate, lithium tetrafluorooxalato phosphate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bisoxalato borate.
11. The lithium ion battery electrolyte of claim 10, wherein the lithium salt comprises one or more of the lithium hexafluorophosphate, the lithium difluorophosphate, the lithium difluorobis oxalato phosphate, and the lithium difluorooxalato borate.
12. The lithium ion battery electrolyte according to claim 10, wherein the mass percentage of the lithium salt in the lithium ion battery electrolyte is 10-20%.
13. A lithium ion battery, comprising:
a housing;
an electrode assembly accommodated within the case; and
the lithium ion battery electrolyte according to any one of claims 1 to 12, which is contained in the housing.
14. The lithium ion battery of claim 13, wherein the battery positive electrode of the electrode assembly satisfies at least one of the following conditions (a) and (b):
(a) The positive electrode active material includes LiNi x Co y Mn z O 2 Wherein x+y+z=1, 0 < x < 1,0 < y < 1,0 < z < 1;
(b) The positive electrode active material includes LiNi 0.5 Mn 1.5 O 4 。
15. The lithium ion battery of claim 13 or 14, wherein in the battery negative electrode of the electrode assembly, the negative electrode active material comprises one or more of graphite, graphite composite, and silicon oxide.
16. The lithium ion battery of claim 15, wherein the negative electrode active material comprises one or more of the graphite and the graphite composite.
17. An electrical device, comprising the lithium ion battery of any one of claims 13-16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN1322025A (en) * | 2000-05-02 | 2001-11-14 | 宇部兴产株式会社 | Non-aqueous storage accumulator with enhanced discharge quantity retaining power |
| JP2004063114A (en) * | 2002-07-25 | 2004-02-26 | Mitsubishi Chemicals Corp | Electrolytic solution and secondary battery |
| CN104051787A (en) * | 2014-07-02 | 2014-09-17 | 东莞市凯欣电池材料有限公司 | Non-aqueous electrolyte, preparation method of non-aqueous electrolyte as well as high-voltage lithium ion battery |
| WO2017057963A1 (en) * | 2015-09-30 | 2017-04-06 | 주식회사 엘지화학 | Non-aqueous electrolyte and lithium secondary battery comprising same |
| CN113571771A (en) * | 2021-02-08 | 2021-10-29 | 深圳市研一新材料有限责任公司 | Electrolyte for lithium ion battery, preparation method of electrolyte and lithium ion battery |
| CN115332628A (en) * | 2022-09-22 | 2022-11-11 | 广汽埃安新能源汽车有限公司 | Lithium ion battery electrolyte, lithium ion battery and electric equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1322025A (en) * | 2000-05-02 | 2001-11-14 | 宇部兴产株式会社 | Non-aqueous storage accumulator with enhanced discharge quantity retaining power |
| JP2004063114A (en) * | 2002-07-25 | 2004-02-26 | Mitsubishi Chemicals Corp | Electrolytic solution and secondary battery |
| CN104051787A (en) * | 2014-07-02 | 2014-09-17 | 东莞市凯欣电池材料有限公司 | Non-aqueous electrolyte, preparation method of non-aqueous electrolyte as well as high-voltage lithium ion battery |
| WO2017057963A1 (en) * | 2015-09-30 | 2017-04-06 | 주식회사 엘지화학 | Non-aqueous electrolyte and lithium secondary battery comprising same |
| CN113571771A (en) * | 2021-02-08 | 2021-10-29 | 深圳市研一新材料有限责任公司 | Electrolyte for lithium ion battery, preparation method of electrolyte and lithium ion battery |
| CN115332628A (en) * | 2022-09-22 | 2022-11-11 | 广汽埃安新能源汽车有限公司 | Lithium ion battery electrolyte, lithium ion battery and electric equipment |
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