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CN110828893A - Lithium ion battery electrolyte and lithium ion battery - Google Patents

Lithium ion battery electrolyte and lithium ion battery Download PDF

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CN110828893A
CN110828893A CN201810900778.6A CN201810900778A CN110828893A CN 110828893 A CN110828893 A CN 110828893A CN 201810900778 A CN201810900778 A CN 201810900778A CN 110828893 A CN110828893 A CN 110828893A
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electrolyte
total mass
carbonate
additive
percent
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CN110828893B (en
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陈黎
王婷婷
甘朝伦
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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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Abstract

The invention relates to a lithium ion battery electrolyte, which comprises lithium salt, an organic solvent and an additive, wherein the additive comprises one or more of substances shown as a general formula (1) or a general formula (2), and the general formula (1) is as follows:
Figure DDA0001759318040000011
general formula (2) is
Figure DDA0001759318040000012
Wherein R1 and R3 are independently hydrogen, alkyl, alkoxy, haloalkyl, phenyl, phenoxy, halophenyl, hydroxy, alkylhydroxy, haloalkylhydroxy, cyano, alkylcyano, haloalkylcyano, silyl, siloxy, silyl, halosilyl, alkylcarboxyl or
Figure DDA0001759318040000013
Wherein R is4、R5Independently is alkyl, phenyl or alkyl hydroxyl, and n is an integer between 0 and 10; r2 is one of alkyl, alkoxy and halogenated alkyl with less than 6 carbons. The non-aqueous electrolyte can further improve the cycle performance, high-temperature storage performance and high-pressure resistance of the lithium ion battery.

Description

Lithium ion battery electrolyte and lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte and a lithium ion battery.
Background
The lithium ion battery has the advantages of light weight, high working voltage, large specific energy density, long cycle life, low self-discharge rate, no memory effect, small environmental pollution and the like, is a green high-energy environment-friendly battery, and is widely applied to the aspects of mobile phones, notebook computers, video cameras, digital cameras, electric automobiles and the like. The electrolyte is an important component of the lithium ion battery, and consists of a solvent, lithium salt and an additive, particularly, the improvement of the additive can give consideration to the comprehensive performance of the lithium ion battery, in the first charging process of the battery, lithium ions are extracted from lithium metal oxide of a cathode active substance and migrate to an anode under the drive of voltage, and the electrolyte reacts with the surface of the anode to produce Li2CO3，Li2O, LiOH, etc., thereby forming a passivation film (SEI) on the surface of the anode. Meanwhile, a reaction also occurs at the cathode to generate a protective film CEI, and since lithium ions must pass through the SEI and CEI films regardless of charge or discharge, the properties of the film determine many properties of the battery (e.g., cycle performance, high-temperature performance, rate performance). Among many additives, succinic anhydride compounds have been considered as a good functional additive, and an electrolyte solution formed with an organic solvent can form a stable and dense Solid Electrolyte Interface (SEI) film on an anode, with good cycle performance. However, with the development of science and technology, the performance requirements of lithium ion batteries are further improved, more additives with better comprehensive performance appear, and the invention patent with the application number of 201710066148.9 discloses a thiodiglycolic anhydride as an additive, which improves the storage, hot box and overcharge performances of the batteries. However, the cycle performance, high-temperature storage performance and high-voltage resistance of lithium ion batteries are still required to be improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing an electrolyte and a lithium ion battery, wherein the electrolyte can improve the cycle performance, the high-temperature storage performance, the high-pressure resistance and the safety performance of the lithium ion battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention aims to provide a lithium ion battery electrolyte, which comprises lithium salt, an organic solvent and an additive, wherein the additive comprises one or more of substances shown as a general formula (1) or a general formula (2),
the general formula (1) is as follows:
Figure BDA0001759318030000021
the general formula (2) is
Figure BDA0001759318030000022
Wherein R1 and R3 are independently hydrogen, alkyl, alkoxy, haloalkyl, phenyl, phenoxy, halophenyl, hydroxy, alkylhydroxy, haloalkylhydroxy, cyano, alkylcyano, haloalkylcyano, silyl, siloxy, silyl, halosilyl, alkylcarboxyl or
Figure BDA0001759318030000023
Wherein R is4、R5Independently is alkyl, phenyl or alkyl hydroxyl, and n is an integer between 0 and 10; r2 is one of alkyl, alkoxy and halogenated alkyl with less than 6 carbons.
Preferably, the substance represented by the general formula (1) or the general formula (2) is:
Figure BDA0001759318030000031
further preferably, the substance represented by the general formula (1) or the general formula (2) is:
Figure BDA0001759318030000032
most preferably, the substance represented by the general formula (1) is:
Figure BDA0001759318030000041
preferably, the feeding mass of one or more of the substances shown in the general formula (1) or the general formula (2) is 0.05-5% of the total mass of the electrolyte.
More preferably, the feeding mass of one or more of the substances shown in the general formula (1) or the general formula (2) is 0.1-2% of the total mass of the electrolyte.
Preferably, the organic solvent is one or more of fluorinated or unsubstituted carbonate, fluorinated or unsubstituted carboxylate, fluorinated or unsubstituted ether, fluorinated or unsubstituted sulfone and fluorinated or unsubstituted sulfoxide, and the feeding mass of the organic solvent is 70-85% of the total mass of the electrolyte.
Further preferably, the organic solvent is one or more of fluoroethylene carbonate, difluoroethylene carbonate, trifluoroethyl carbonate, fluoroethylene sulfone, tetrafluoroethyl tetrafluoropropyl ether, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethyl methyl carbonate, ethylene glycol dimethyl ether, r-butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, sulfolane, methyl ethyl sulfone, dimethyl sulfoxide.
More preferably, the feeding mass of the organic solvent is 80-85% of the total mass of the electrolyte.
Preferably, the lithium salt is LiPF6、LiBF4、LiAsF6、LiClO4、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、Li(CF3SO2)3C、Li(C6F5)4B、Li(C2F5SO2)2N、LiBF3C2F5、LiPF3(C2F5)3The charging mass of the lithium salt is 10-25% of the total mass of the electrolyte.
More preferably, the feeding mass of the lithium salt is 10-15% of the total mass of the electrolyte.
Further preferably, the lithium salt is LiPF6。
Preferably, the additive further comprises other additives, the other additives are one or more of cyclic carbonate containing double bonds, cyclic carbonate containing halogen, sulfonate, sultone, sulfate, sulfite, benzene compound, fluorobenzene compound, nitrile compound, cyclic ether compound, phosphazene compound, phosphate, boron compound, amine compound, silicon-containing compound and lithium salt type additive, and the feeding mass of the other additives is 0.5-5% of the total mass of the electrolyte.
Further preferably, the other additive is vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, methylene methanedisulfonate, vinyl sulfate, vinyl sulfite, 1, 3-propane sultone, 1, 3-dioxane, biphenyl, cyclohexylbenzene, tert-butylbenzene, tert-pentylbenzene, m-fluorotoluene, 3, 4-difluorotoluene, 4-bromo-2-fluorophenylmethyl ether, p-fluorotoluene, p-xylene, 1, 2-dimethoxy-4-nitrobenzene, N-phenylmaleimide, pentafluoroanisole, 2, 5-di-tert-butyl, 1, 4-dimethoxybenzene, adiponitrile, hexanetrinitrile, succinonitrile, N-butylamine, methanolamine, ethanolamine, N-dicyclohexylimine, N-diethylaminotrimethylsilane, carbodiimide, N-diethyltrimethylsilane, or a mixture thereof, Hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, triphenyl phosphate, adiponitrile, pimelonitrile, ethoxypentafluorotriphosphazene, lithium dioxalate borate, lithium oxalyldifluoroborate, lithium difluorophosphate, lithium difluorobisoxalato phosphate, tris (trimethylsilane) borate, tris (trimethylsilane) phosphate.
More preferably, the feeding mass of the other additives is 3-4% of the total mass of the electrolyte.
The invention also aims to provide a lithium ion battery, which comprises a shell, a battery core and a non-aqueous electrolyte, wherein the battery core and the non-aqueous electrolyte are accommodated in the shell; the battery core comprises a positive electrode, a negative electrode and a diaphragm between the positive electrode and the negative electrode, and the non-aqueous electrolyte is the lithium ion battery electrolyte.
Preferably, the positive electrode comprises a positive electrode current collector and a positive electrode material located on the surface of the positive electrode current collector, the positive electrode material comprises a positive electrode active substance, a positive electrode conductive agent and a positive electrode binder, and the positive electrode active substance can be LiNi0.5Mn1.5O4、LiNiPO4、LiCoPO4、Li3V2(PO4)3、LiNi1-xMnxO2、LiNi1-xCoxO2、LiNi1-y-zCoyMnzO2Or LiNi1-y-zCoyAlzO2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0, z is more than or equal to 0, and y + z is less than or equal to 1.
More preferably, the positive electrode active material is LiNi0.5Co0.2Mn0.3O2(NCM)。
Further preferably, the positive electrode conductive agent is acetylene black or carbon nanotubes, and the positive electrode binder is polyvinylidene fluoride.
Preferably, the negative electrode comprises a negative electrode current collector and a negative electrode material located on the surface of the negative electrode current collector, the negative electrode material comprises a negative electrode active material and a negative electrode binder, the negative electrode material may also optionally comprise a negative electrode conductive agent, the negative electrode conductive agent and the positive electrode conductive agent may be the same or different and are conductive agents commonly used in the art, the negative electrode active material and the negative electrode binder may be negative electrode active materials and negative electrode binders commonly used in the art, for example, the negative electrode active material may be metal lithium, metal oxide, lithium aluminum alloy, graphite and modified carbon materials, silicon and silicon-oxygen and silicon-carbon thereof. Preferably, the negative electrode active material is graphite.
In particular, the separator layer is a separator layer conventionally used in the art.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, through research, two sulfur group-containing succinic anhydride compounds (1) and (2) with a structural general formula are found, and an organic solvent, a lithium salt and other additives in the non-aqueous electrolyte are combined and optimized, so that the non-aqueous electrolyte can further improve the cycle performance, the high-temperature storage performance and the high-pressure resistance performance of the lithium ion battery.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Comparative example 1
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 34% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte.
Example 1
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, and the additive cyclohexylbenzene accounts for 1 percent of the total mass of the electrolyteThe total mass percent is 0.2 percent, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass percent of the electrolyte. Additive agent
Figure BDA0001759318030000061
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 2
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000071
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 3
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000072
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 4
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000081
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 5
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000082
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 6
The non-aqueous organic solvent is ethylene carbonate or diethyl carbonateThe mass ratio of the methyl ethyl carbonate to the methyl ethyl carbonate in the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000091
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 7
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000092
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 8
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, and the additive lithium difluoro oxalate borate accounts for the total mass of the electrolyteThe percentage of the additive is 0.3%, the additive lithium difluorophosphate accounts for 0.5% of the total mass of the electrolyte, the additive is fluoroethylene carbonate accounts for 1% of the total mass of the electrolyte, the additive is 1, 3-propane sultone accounts for 1.0% of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2% of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5% of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000093
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 9
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000101
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 10
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, and the additive 1, 3-propane sultone accounts for the total mass of the electrolyteThe percentage is 1.0 percent, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000102
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 11
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000111
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 12
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000112
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 13
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluoro oxalate borate accounts for 0.3 percent of the total mass of the electrolyte, the additive lithium difluoro phosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 1.0 percent of the total mass of the electrolyte, the additive cyclohexylbenzene accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexanetricarbonitrile accounts for 0.5 percent of the total mass of the electrolyte. Additive agent
Figure BDA0001759318030000121
And
Figure BDA0001759318030000122
respectively accounting for 0.5 percent of the total mass of the electrolyte.
Results of the experiment
The electrolytes obtained in comparative example 1 and examples 1 to 13 were injected into LiNi of the same lot0.5Co0.2Mn0.3O2In 1Ah polymer pouch cells (NCM), the cells were tested for cycle life at room temperature of 4.2V and 4.25V (table 1), for swelling and internal resistance change at 60 ° high temperature for 7 days (table 2), and for overcharge at 3C, 10V (table 3), with the following specific results:
TABLE 1
Figure BDA0001759318030000123
Figure BDA0001759318030000131
TABLE 2
Standing at 60 ℃ for 7 days (bulging percentage%) Standing at 60 deg.C for 7 days (internal resistance change rate%)
Comparative example 1 24.91 52.68
Example 1 16.44 44.94
Example 2 19.07 47.05
Example 3 20.38 48.37
Example 4 18.65 48.27
Example 5 19.29 48.16
Example 6 21.46 50.44
Example 7 21.97 50.85
Example 8 17.30 46.21
Example 9 18.14 48.63
Example 10 21.64 49.93
Example 11 17.78 46.26
Example 12 16.58 45.80
Example 13 18.05 46.73
TABLE 3
Figure BDA0001759318030000132
Figure BDA0001759318030000141
As can be seen from the above table, the examples of the present invention are superior to the batteries prepared in the comparative examples in both the shelf life at normal temperature and high temperature and in the high pressure resistance.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (10)

1. The lithium ion battery electrolyte comprises lithium salt, an organic solvent and an additive, and is characterized in that: the additive comprises one or more of substances shown as a general formula (1) or a general formula (2),
the general formula (1) is as follows:
Figure FDA0001759318020000011
the general formula (2) is
Figure FDA0001759318020000012
Wherein R1 and R3 are independently hydrogen, alkyl, alkoxy, haloalkyl, phenyl, phenoxy, halophenyl, hydroxy, alkylhydroxy, haloalkylhydroxy, cyano, alkylcyano, haloalkylcyano, silyl, siloxy, silyl, halosilyl, alkylcarboxyl or
Figure FDA0001759318020000013
Wherein R is4、R5Independently is alkyl, phenyl or alkyl hydroxyl, and n is an integer between 0 and 10; r2 is one of alkyl, alkoxy and halogenated alkyl with less than 6 carbons.
2. The lithium ion battery electrolyte of claim 1, wherein: the substance shown as the general formula (1) or the general formula (2) is:
Figure FDA0001759318020000021
3. the lithium ion battery electrolyte of claim 1 or 2, wherein: the feeding mass of one or more of the substances shown in the general formula (1) or the general formula (2) is 0.05-5% of the total mass of the electrolyte.
4. The lithium ion battery electrolyte of claim 3, wherein: the feeding mass of one or more of the substances shown in the general formula (1) or the general formula (2) is 0.1-2% of the total mass of the electrolyte.
5. The lithium ion battery electrolyte of claim 1, wherein: the organic solvent is one or more of fluorinated or unsubstituted carbonate, fluorinated or unsubstituted carboxylic ester, fluorinated or unsubstituted ether, fluorinated or unsubstituted sulfone and fluorinated or unsubstituted sulfoxide, and the feeding mass of the organic solvent is 70-85% of the total mass of the electrolyte.
6. The lithium ion battery electrolyte of claim 5, wherein: the organic solvent is one or more of fluoroethylene carbonate, difluoroethylene carbonate, trifluoroethyl carbonate, fluoroethyl sulfone, tetrafluoroethyl tetrafluoropropyl ether, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, methyl ethyl carbonate, ethylene glycol dimethyl ether, r-butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, sulfolane, methyl ethyl sulfone and dimethyl sulfoxide, and the feeding mass of the organic solvent is 80-85% of the total mass of the electrolyte.
7. The lithium ion battery electrolyte of claim 1, wherein: the lithium salt is LiPF6、LiBF4、LiAsF6、LiClO4、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、Li(CF3SO2)3C、Li(C6F5)4B、Li(C2F5SO2)2N、LiBF3C2F5、LiPF3(C2F5)3The charging mass of the lithium salt is 10-25% of the total mass of the electrolyte.
8. The lithium ion battery electrolyte of claim 1, wherein: the additive also comprises other additives, wherein the other additives are one or more of double-bond-containing cyclic carbonate, halogen-containing cyclic carbonate, sulfonate, sultone, sulfate, sulfite, benzene compound, fluorobenzene compound, nitrile compound, cyclic ether compound, phosphazene compound, phosphate, boron compound, amine compound, silicon-containing compound and lithium salt type additive, and the feeding mass of the other additives is 0.5-5% of the total mass of the electrolyte.
9. The lithium ion battery electrolyte of claim 8, wherein: the other additives are vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, methylene methanedisulfonate, vinyl sulfate, vinyl sulfite, 1, 3-propanesultone, 1, 3-dioxane, biphenyl, cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, m-fluorotoluene, 3, 4-difluorotoluene, 4-bromo-2-fluorophenylmethyl ether, p-fluorotoluene, p-xylene, 1, 2-dimethoxy-4-nitrobenzene, N-phenylmaleimide, pentafluoroanisole, 2, 5-di-tert-butyl, 1, 4-dimethoxybenzene, adiponitrile, hexanetrinitrile, succinonitrile, N-butylamine, methanolamine, ethanolamine, N-dicyclohexylcarbodiimide, N-diethylamine trimethylsilane, hexamethyldisilazane, dimethylmethane disulfonate, ethylene sulfate, vinyl sulfite, 1, 3-propane sultone, p-xylene, 1, 2-dimethoxy-4-nitrobenzene, N-phenyl maleimide, p-fluorobenzene, p-xylene, The electrolyte is prepared from one or more of hexaethyldisilazane, hexapropyldisilazane, triphenyl phosphate, adiponitrile, pimelonitrile, ethoxy pentafluorotriphosphazene, lithium dioxalate borate, lithium oxalyldifluoroborate, lithium difluorophosphate, lithium difluorobisoxalato phosphate, tris (trimethylsilane) borate and tris (trimethylsilane) phosphate, and the feeding mass of other additives is 3-4% of the total mass of the electrolyte.
10. A lithium ion battery comprises a shell, a battery core and a non-aqueous electrolyte, wherein the battery core and the non-aqueous electrolyte are accommodated in the shell; the battery core comprises a positive electrode, a negative electrode and a diaphragm between the positive electrode and the negative electrode, and is characterized in that: the nonaqueous electrolytic solution is the lithium ion battery electrolyte according to any one of claims 1 to 9.
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