CN112216870B - High-temperature-resistant high-voltage electrolyte for high-nickel lithium ion battery - Google Patents
High-temperature-resistant high-voltage electrolyte for high-nickel lithium ion battery Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 7
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- KAEZJNCYNQVWRB-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] KAEZJNCYNQVWRB-UHFFFAOYSA-K 0.000 claims abstract 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 15
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 11
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 abstract description 2
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910013872 LiPF Inorganic materials 0.000 description 8
- 101150058243 Lipf gene Proteins 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/0042—Four or more solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The high-temperature and high-voltage resistant electrolyte of the high-nickel lithium ion battery consists of a composite electrolyte lithium salt, an organic multi-component solvent and an additive, wherein the composite electrolyte lithium salt is at least two of lithium salts such as lithium hexafluorophosphate, lithium perchlorate, lithium difluorophosphate, lithium difluorosulfimide, lithium dioxalate borate, lithium difluorooxalate borate and lithium difluorooxalate phosphate. The electrolyte lithium salt and the additive in the electrolyte simultaneously participate in positive electrode film formation to prevent the electrolyte from contacting with the electrode, so that decomposition reaction of the electrolyte and active substances in a high-potential area is inhibited, and the storage and circulation performance of the lithium ion battery under high temperature and high voltage is improved.
Description
Technical Field
The invention relates to electrolyte of a lithium ion battery, in particular to high-temperature and high-voltage resistant electrolyte of a high-nickel lithium ion battery.
Background
With the development of new energy markets, the improvement of the energy density of lithium ion power batteries is urgent. High nickel ternary positive electrode material (nickel content is above 60%), compared with currently used LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM 523) materials, which have higher specific capacity and lower cost, and high charge/discharge capacity at high voltage, greatly improve the energy density of lithium batteries, and thus attract wide attention. However, under high temperature cycle, ni in the high nickel positive electrode material 3+ Is easy to be reduced into Ni 2+ Occupying lithium layer vacancy to generate cation mixed arrangement, and the material is easy to generate phase structure transformation (layered- & gt spinel- & gt rock salt) to form electrochemical inert NiO-like phase, so that free deintercalation of lithium ions is affected; and the self-discharge phenomenon of the high-nickel ternary positive electrode material at high temperature is serious, the capacity loss and the battery expansion are easy to cause, and the storage life of the battery is shortened. In addition, under high voltage, ni 4+ Is easy to be developed with electrolyteSevere side reactions occur, which cause the material structure to be damaged and release oxygen and heat, so that the cycle performance and thermal stability of the electrode material are deteriorated, and the safety performance of the lithium ion battery is lowered.
CN110649319a discloses a high temperature resistant electrolyte matching a high nickel positive electrode material lithium ion battery, but does not show how high temperature performance of the high nickel positive electrode material performs for high voltage conditions.
Therefore, development of an electrolyte which can both realize high temperature and high pressure resistance has important significance for improving the energy density of the battery.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the electrolyte which can relieve the high-temperature self-discharge phenomenon of the high-nickel lithium ion battery and improve the long-cycle performance of the high-voltage high-nickel lithium ion battery.
The technical scheme adopted by the invention for solving the technical problems is that the high-temperature and high-voltage resistant electrolyte of the high-nickel lithium ion battery consists of a composite electrolyte lithium salt, an organic multi-component solvent and an additive.
Further, the composite electrolyte lithium salt is lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium difluorophosphate (LiPO) 2 F 2 ) At least two of lithium difluorosulfimide (LiFSI), lithium dioxalate borate (LiBOB), lithium difluorooxalato borate (LiODFB) and lithium difluorooxalato phosphate (LiODFP). The metal ions of the high-nickel anode material are obviously dissolved out in a high-temperature environment, and the dissolved metal ions have decomposition and catalysis effects on additives and solvents, and the anode film-forming additives such as novel lithium salt fluorocarbon lithium sulfonate, sulfur system, phosphorus system and the like have better anode film-forming functions.
Further, the mass fraction of the composite electrolyte lithium salt is 11-25%. The mass fraction of the lithium salt is increased, and the free ions generated by electrolysis are increased, so that the conductivity is increased; but at the same time the viscosity of the electrolyte and the extent of ionic association will increase with increasing mass fraction of lithium salt, which in turn will decrease the conductivity. Too low a mass fraction of lithium salt can result in too little lithium ion in the electrolyte, too low conductivity, and poor all performance of the lithium battery, particularly poor long cycle performance.
Further, the organic multi-component solvent is formed by mixing more than 5 of Ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl Acetate (MA), methyl Butyrate (MB), gamma-butyrolactone (GBL), fluorobenzene (FB) and fluoroethylene carbonate (FEC) (according to the number of organic solvent varieties, the organic solvents can be respectively called as a five-membered organic solvent, a six-membered organic solvent, a seven-membered organic solvent and the like). In order to meet various demands such as an operating temperature range and electrical conductivity, a cyclic carbonate having a high dielectric constant and a chain carbonate having a low viscosity are generally mixed and used.
Further, the five-membered organic solvent is formed by mixing 5 organic solvents, and the proportion of the components is 1:1-2:4-5:4-5:8-9 according to the mass ratio.
Further, the additive is at least two of Vinylene Carbonate (VC), ethylene carbonate (VEC), 1, 3-Propane Sultone (PS), propenyl Sultone (PST), vinyl sulfate (DTD), triallyl phosphate (TAP), tris (trimethylsilane) phosphite (TMSPi), tris (trimethylsilane) phosphate (TMSP). Film forming additives in the electrolyte affect the cycle life of the battery, and are also extremely important and indispensable.
Further, the total mass fraction of the additive is 0.5-6%. Excessive addition can lead to high viscosity, low conductivity, high impedance and obvious cost increase of the electrolyte; too small an amount of the additive cannot ensure the film forming effect, resulting in failure to achieve the expected improvement effect of the electrical properties.
The invention has the following beneficial effects: the composite electrolyte lithium salt and the additive participate in the positive electrode film forming, a conductive passivation film is formed on the surface of the positive electrode, and the contact between the electrolyte and the electrode is reduced, so that the decomposition reaction of the electrolyte and the active substance in a high potential area is inhibited, the stability of the positive electrode material is improved, and meanwhile, the deintercalation of lithium ions is not influenced. In addition, the solvent with a higher electrochemical window is used for inhibiting the decomposition of electrolyte, so that the high-temperature performance and the cycle performance of the high-nickel cathode material lithium ion battery are improved.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1
The electrolyte composition of this example was: the lithium salt part adopts 13.75% of LiPF by mass 6 、1%LiPO 2 F 2 And 2% lifsi; the solvent part adopts EC, PC, DEC, EMC, DMC, and the corresponding mass percentage is 25:5:20:45:5; the additive part adopts the weight fraction of 0.8% VC and 0.4% PS respectively.
The electrolyte is mixed in a closed environment with the water oxygen content less than or equal to 1 ppm; fully and uniformly mixing (the same applies below).
Example 2
The electrolyte composition of this example was: the lithium salt part adopts 13.75% of LiPF by mass 6 、1%LiPO 2 F 2 And 2% lifsi complex; the solvent part adopts EC, PC, DEC, EMC, DMC, and the corresponding mass percentage is 25:5:20:45:5; the additive parts are respectively 0.8% VC, 0.2% VEC, 0.4% PS and 0.3% PST by mass fraction.
Example 3
The electrolyte composition of this example was: the lithium salt part adopts 13.75% of LiPF by mass 6 、1%LiPO 2 F 2 And 2% lifsi complex; the solvent part adopts EC, PC, DEC, EMC, DMC, and the corresponding mass percentage is 25:5:20:45:5; the additive parts are respectively 0.8% VC, 0.2% VEC, 0.4% PS, 0.3% PST and 0.3% TAP by mass fraction.
Example 4
The electrolyte composition of this example was: the lithium salt part adopts 13.75% of LiPF by mass 6 、1%LiPO 2 F 2 And 2% lifsi complex; the solvent part adopts EC, PC, DEC, EMC, DMC, and the corresponding mass percentage is 25:5:20:45:5; the additive part adopts the mass fractions of 0.8% VC, 0.2% VEC, 0.4% PS, 0.3% PST and 1% DTD respectively.
Example 5
The electrolyte composition of this example was: the lithium salt part adopts 13.75% of LiPF by mass 6 、1%LiPO 2 F 2 A complex of 2% lifsi and 0.3% liodfp; the solvent part adopts EC, PC, DEC, EMC, DMC, and the corresponding mass percentage is 25:5:20:45:5; the additive parts are respectively 0.8% VC, 0.2% VEC, 0.4% PS and 0.3% PST by mass fraction.
Example 6
The electrolyte composition of this example was: the lithium salt part adopts 13.75% of LiPF by mass 6 、1%LiPO 2 F 2 A complex of 2% lifsi and 0.3% liodfp; the solvent part adopts EC, PC, DEC, EMC, DMC, and the corresponding mass percentage is 25:5:20:45:5; the additive parts are respectively 0.8% VC, 0.2% VEC, 0.4% PS, 0.3% PST, 0.3% TAP and 1% DTD by mass fraction.
Comparative example
The electrolyte composition of this example was: the lithium salt part adopts LiPF with the mass fraction of 13.75 percent 6 The method comprises the steps of carrying out a first treatment on the surface of the The solvent part adopts EC, PC, DEC, EMC, DMC, and the corresponding mass percentage is 25:5:20:45:5; the additive part adopts the weight fraction of 0.8% VC and 0.4% PS respectively.
Electrochemical performance test
The electrolytes prepared in examples 1 to 6 of the present invention and comparative example were injected into LiNi respectively 0.8 Co 0.1 Mn 0.1 O 2 After the lithium ion battery of the material system is subjected to high-temperature storage at 60 ℃ and high-temperature cycle test, the test flow is as follows:
high temperature storage test at 60 ℃): charging to 4.4V with 1C current at constant current and constant voltage, stopping charging when the current is reduced to 0.05C current, and standing for 1h; the cells were stored in an incubator at 60 ℃ ± 2 ℃ for 7 days, 15 days and 30 days, respectively; after expiration of the storage period, the battery was taken out of the incubator to test its volume expansion rate, capacity retention rate and recovery rate.
TABLE 1 data for testing the electrical properties of the electrolytes of examples 1-6 and comparative example of the present invention at 60℃high temperature
High temperature cycle test at 60 ℃): in a 60 ℃ incubator, the battery is charged to 4.4V by adopting a constant current and a constant voltage of 0.5C, the charging is stopped when the current is reduced to 0.05C, and the battery is placed for 10min, then is discharged to 3.0V by adopting a constant current of 0.5C, and is placed for 10min after discharging, and the battery is circulated in one process step until the discharge capacity is lower than 80% of the initial capacity.
TABLE 2 data for high temperature cycle test at 60℃for the electrolytes of examples 1-6 and comparative example of the present invention
From the test data listed in tables 1 and 2 above, it can be seen that: compared with the lithium battery prepared from the electrolyte of the comparative examples, the lithium battery prepared from the electrolyte of the examples 1-6 of the invention has the advantages that the thermal stability of the high-nickel positive electrode material is greatly improved due to the fact that a certain amount of positive electrode film forming additive is used in the examples 1-6, so that the storage performance and the cycle performance of the battery are obviously better than those of the comparative examples at the high temperature of 60 ℃.
Claims (2)
1. The high-temperature and high-voltage resistant electrolyte of the high-nickel lithium ion battery is characterized by comprising a composite electrolyte lithium salt, an organic multi-component solvent and an additive;
the composite electrolyte lithium salt comprises 13.75% of lithium hexafluorophosphate, 1% of lithium difluorophosphate and 2% of lithium difluorosulfimide by mass fraction;
the additive is ethylene carbonate with the mass fraction of 0.8 percent, ethylene carbonate with the mass fraction of 0.2 percent, 1, 3-propane sultone with the mass fraction of 0.4 percent, propenyl sultone with the mass fraction of 0.3 percent and triallyl phosphate with the mass fraction of 0.3 percent;
the organic multi-component solvent is ethylene carbonate, propylene carbonate, diethyl carbonate, methyl ethyl carbonate and dimethyl carbonate, and the corresponding mass percentage is 25:5:20:45:5.
2. The high-temperature and high-voltage resistant electrolyte of the high-nickel lithium ion battery is characterized by comprising a composite electrolyte lithium salt, an organic multi-component solvent and an additive;
the composite electrolyte lithium salt comprises 13.75% of lithium hexafluorophosphate, 1% of lithium difluorophosphate, 2% of lithium difluorosulfimide and 0.3% of lithium difluorooxalate phosphate by mass fraction;
the additive is composed of, by mass, 0.8% of vinylene carbonate, 0.2% of ethylene carbonate, 0.4% of 1, 3-propane sultone, 0.3% of propenyl sultone, 0.3% of triallyl phosphate and 1% of vinyl sulfate;
the organic multi-component solvent is ethylene carbonate, propylene carbonate, diethyl carbonate, methyl ethyl carbonate and dimethyl carbonate, and the corresponding mass percentage is 25:5:20:45:5.
Priority Applications (1)
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| EP4145580A4 (en) * | 2021-07-22 | 2023-11-01 | Contemporary Amperex Technology Co., Limited | Electrolyte, lithium-ion battery, and power device |
| CN114006044A (en) * | 2021-10-25 | 2022-02-01 | 惠州亿纬锂能股份有限公司 | High-voltage electrolyte and application thereof |
| CN114204123A (en) * | 2021-12-10 | 2022-03-18 | 湖南航天磁电有限责任公司 | High-voltage-resistant high-power electrolyte and application thereof |
| CN114221032A (en) * | 2021-12-16 | 2022-03-22 | 湖北亿纬动力有限公司 | Lithium ion battery electrolyte and preparation method and application thereof |
| CN115602922A (en) * | 2022-10-24 | 2023-01-13 | 江西远东电池有限公司（Cn） | High-nickel silicon-based lithium ion battery electrolyte and cylindrical high-nickel silicon-based lithium ion battery |
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