CN109980278B - Electrolyte and secondary lithium battery - Google Patents

Electrolyte and secondary lithium battery Download PDF

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CN109980278B
CN109980278B CN201711456886.0A CN201711456886A CN109980278B CN 109980278 B CN109980278 B CN 109980278B CN 201711456886 A CN201711456886 A CN 201711456886A CN 109980278 B CN109980278 B CN 109980278B
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additive
electrolyte
chloride
total mass
percent
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CN109980278A (en
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陈黎
甘朝伦
陈晓荣
王婷婷
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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
    • H01M10/052—Li-accumulators
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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

Abstract

The invention relates toThe electrolyte comprises lithium salt, a non-aqueous solvent and an additive, wherein the additive comprises one or more of an additive I, an additive II, an additive III and an additive IV, the structural general formula of the additive I is R1-B ═ O, and the structural general formula of the additive II is
Figure DDA0001529426040000011
The general structural formula of the additive III is
Figure DDA0001529426040000012
The general structural formula of the additive IV is

Description

Electrolyte and secondary lithium battery
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to an electrolyte and a secondary lithium battery.
Background
The lithium ion battery is a green high-energy environment-friendly battery appearing in 90 s of the 20 th century, and has the advantages of high voltage, small volume, light weight, high specific energy, no memory effect, no pollution, small self-discharge, long service life and the like, so that the lithium ion battery is rapidly popularized in portable electronic products which emphasize lightness, thinness, shortness and multiple functions, such as mobile phones, notebook computers, video cameras, digital cameras and the like.
In the first charging process of the lithium ion battery, lithium ions are extracted from lithium metal oxide of a cathode active material and migrate to an anode under the driving of voltage, and an 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. Since lithium ions must pass through the SEI film regardless of charging or discharging, the properties of the SEI film determine the versatility of the batteryEnergy (such as cycle performance, high temperature performance, rate performance). On the other hand, it is desirable that the electrolyte reacts with the surface of the lithium metal oxide cathode to form a protective film having a low resistance, and that the elution of metal ions due to oxidative decomposition of the cathode material can be suppressed without affecting the migration and diffusion of lithium ions.
Lithium bis (oxalato) borate and lithium difluoro (oxalato) borate are one of novel organic boric acid compounds developed recently, have good thermal stability and electrochemical stability, and can form a stable and compact Solid Electrolyte Interface (SEI) film on an anode in an electrolyte solution formed by the lithium bis (oxalato) borate and the lithium difluoro (oxalato) borate and an organic solvent, so that the lithium bis (oxalato) borate and the lithium difluoro (oxalato) borate have good cycle performance. However, these compounds have not achieved satisfactory technical effects in terms of physical properties and chemical characteristics.
With the development of technology, the performance requirements of lithium ion batteries are further increased, and therefore, research on more substances containing boron and oxygen is necessary to obtain lithium ion batteries with better performance.
Disclosure of Invention
The invention aims to provide an electrolyte capable of improving the cycle performance, high-temperature storage performance, high-pressure resistance and safety performance of a secondary lithium battery.
The invention also provides a secondary lithium battery adopting the electrolyte.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention aims to provide an electrolyte, which comprises lithium salt, a non-aqueous solvent and an additive, wherein the additive comprises one or more of an additive I, an additive II, an additive III and an additive IV,
the structural general formula of the additive I is R1-B ═ O, wherein R1 is phenyl, halogenated phenyl, phenylalkanochloride or halogenated phenylalkanochloride;
the general structural formula of the additive II is
Figure BDA0001529426030000011
Wherein R2, R3, R4,R5 is independently hydroxy, phenyl, halogen, alkyl, alkoxy, phenoxy, haloalkyl, halophenyl, phenylalkyl ether, or halophenylalkyl ether and at least one of R2, R3, R4, R5 is phenyl, phenoxy, halophenyl, phenylalkyl ether, or halophenylalkyl ether;
the general structural formula of the additive III is
Figure BDA0001529426030000021
Wherein R6, R7 and R8 are independently hydrogen, hydroxyl, phenyl, alkyl, phenyl alkanoyl chloride or halogenated phenyl alkanoyl chloride, at least one of R6, R7 and R8 is phenyl, phenyl alkanoyl chloride or halogenated phenyl alkanoyl chloride, and n is an integer of 1-6;
the general structural formula of the additive IV is
Figure BDA0001529426030000022
Wherein R9 is phenyl, phenylalkanochloride or halogenated phenylalkanochloride, and m is an integer of 1-6.
Preferably, R1 is phenylformyl chloride, phenylacetyl chloride, phenylpropionyl chloride, phenylbutyryl chloride, halophenylformyl chloride, halophenylacetyl chloride, halophenylpropionyl chloride, or halophenylbutyryl chloride;
r2, R3, R4 and R5 are independently hydroxyl, phenyl, phenoxy, halophenyl, phenylmethyl ether, phenylethyl ether, phenylpropyl ether, phenylbutyl ether, halophenylmethyl ether, halophenylethyl ether, halophenylpropyl ether or halophenylbutyl ether, and R2, R3, R4 and R5 are not hydroxyl at the same time;
r6, R7 and R8 are independently hydrogen, hydroxyl, phenyl, phenylformyl chloride, phenylacetyl chloride, phenylpropionyl chloride, phenylbutyryl chloride, halophenylformyl chloride, halophenylacetyl chloride, halophenylpropionyl chloride or halophenylbutyryl chloride, at least one of R6, R7 and R8 is phenyl, phenylformyl chloride, phenylacetyl chloride, phenylpropionyl chloride, phenylbutyryl chloride, halophenylformyl chloride, halophenylacetyl chloride, halophenylpropionyl chloride or halophenylbutyryl chloride, and n is an integer of 1-3;
r9 is phenyl, phenylformyl chloride, phenylacetyl chloride, phenylpropionyl chloride, phenylbutyryl chloride, halophenylformyl chloride, halophenylacetyl chloride, halophenylpropionyl chloride or halophenylbutyryl chloride, and m is an integer of 2-4.
In the present invention, halogen used for the halogenation is fluorine, chlorine, bromine or iodine, and preferably fluorine or chlorine.
In the invention, the phenyl alkanoyl chloride means that a benzene ring is connected with B or O, and one substituent on the benzene ring is alkanoyl chloride; the halogenated phenyl alkanoyl chloride means that a benzene ring is connected with B or O, one substituent on the benzene ring is alkanoyl chloride, and the other substituent is halogen; phenyl alkyl ether refers to a benzene ring connected with B or O, and a substituent on the benzene ring is alkyl ether; halogenated phenyl alkyl ether means that a benzene ring is connected with B or O, one substituent on the benzene ring is alkyl ether, and the other substituent is halogen.
Further preferably, the additive I is
Figure BDA0001529426030000031
The additive II is
Figure BDA0001529426030000032
Figure BDA0001529426030000033
One or more of the above; the additive III is
Figure BDA0001529426030000034
The additive IV is
Figure BDA0001529426030000035
Preferably, the feeding mass of one or more of the additive I, the additive II, the additive III and the additive IV accounts for 0.05-5% of the total mass of the electrolyte.
Further preferably, the feeding mass of one or more of the additive I, the additive II, the additive III and the additive IV accounts for 0.1-2% of the total mass of the electrolyte.
More preferably, the feeding mass of one or more of the additive I, the additive II, the additive III and the additive IV accounts for 0.5-1.5% of the total mass of the electrolyte.
Most preferably, the feeding mass of one or more of the additive I, the additive II, the additive III and the additive IV accounts for 0.8-1.2% of the total mass of the electrolyte.
In the invention, the feeding quality of one or more of the additive I, the additive II, the additive III and the additive IV refers to that when only one of the additive I, the additive II, the additive III and the additive IV is adopted, the feeding quality is one quality; when the additive I, the additive II, the additive III and the additive IV are adopted, the feeding mass is the total mass of the additives.
Preferably, the nonaqueous solvent is one or more selected from carbonate, fluoro carbonate, carboxylate, fluoro carboxylate, ether, fluoro ether, sulfone, fluoro sulfone, sulfoxide and fluoro sulfoxide, and the feeding mass of the nonaqueous solvent accounts for 70-85% of the total amount of the electrolyte.
More preferably, the non-aqueous solvent is a mixture of two or more selected from 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, ethyl acetate, sulfolane, methyl ethyl sulfone, and dimethyl sulfoxide.
More preferably, the nonaqueous solvent is a mixture of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate in a mass ratio of 1-2: 1: 1.2-2.2.
More preferably, the mass of the nonaqueous solvent is 80-85% of the total amount of the electrolyte.
Preferably, the lithium salt is selected from LiPF6、LiBF4、LiAsF6、LiClO4、LiBOB、LiDFOB、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、Li(CF3SO2)3C、Li(C6F5)4B、Li(C2F5SO2)2N、LiBF3C2F5、LiPF3(C2F5)3The charging mass of the lithium salt accounts for 10-25% of the total mass of the electrolyte.
Further preferably, the lithium salt is LiPF6。
More preferably, the feeding mass of the lithium salt accounts for 10-15% of the total mass of the electrolyte.
Preferably, the additive further comprises other additives accounting for 0.5-5% of the total mass of the electrolyte, and the other additives are one or more selected from cyclic carbonate containing double bonds, cyclic carbonate containing halogen, anhydride compound, sulfonate, sultone, sulfate, sulfite, benzene compound, fluorobenzene compound, nitrile compound, cyclic ether compound, phosphazene compound, phosphate, boron compound, amine compound and silicon-containing compound.
Further preferably, the other additive is selected from the group consisting of vinylene carbonate, vinyl ethylene carbonate, succinic anhydride, phthalic anhydride, 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, N-butylamine, methanolamine, ethanolamine, N-dicyclohexylcarbodiimide, N-diethylamine trimethylsilane, hexamethyldisilazane, and mixtures thereof, Hexaethyldisilazane, hexapropyldisilazane, triphenyl phosphate, adiponitrile, pimelonitrile, ethoxypentafluorotriphosphazene, lithium dioxalate borate, lithium difluorooxalato borate, tris (trimethylsilane) phosphate, fluoroethylene carbonate, and 1,3, 6-hexanetrinitrile.
It is another object of the present invention to provide a secondary lithium battery using the electrolyte.
The secondary lithium battery also comprises a shell and a battery cell accommodated in the shell, wherein the electrolyte is filled in the shell, and the battery cell comprises a positive electrode, a negative electrode and a diaphragm between the positive electrode and the negative electrode.
Specifically, the positive electrode comprises a positive electrode current collector and a positive electrode material positioned on the surface of the positive electrode current collector, wherein the positive electrode material comprises a positive electrode active substance, a positive electrode conductive agent and a positive electrode binder.
Preferably, the positive active material of the secondary lithium battery is selected from LiNi0.5Mn1.5O4、LiNiPO4、LiCoPO4、Li3V2(PO4)3、LiNi1-xMnxO2、LiNi1-xCoxO2、LiNi1-y-zCoyMnzO2、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 LiNi0.8Co0.15Al0.05O2(NCA)。
Further preferably, the positive electrode conductive agent is acetylene black or carbon nanotubes, and the positive electrode binder is polyvinylidene fluoride.
Specifically, 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 can also optionally comprise a negative electrode conductive agent, the negative electrode conductive agent and the positive electrode conductive agent can be the same or different and are conductive agents commonly used in the field, the negative electrode active material and the negative electrode binder can be negative electrode active materials and negative electrode binders commonly used in the field, for example, the negative electrode active material can be metal lithium, metal oxide, lithium aluminum alloy, graphite, modified carbon material, silicon oxide thereof, and silicon carbon. 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:
the electrolyte can comprehensively improve the cycle performance, high-temperature storage performance, high-pressure resistance and safety performance of a secondary lithium 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. In this specification, "%" represents mass% unless otherwise specified.
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-oxalato-borate accounts for 0.3 percent of the total mass of the electrolyte, the additive fluoroethylene carbonate accounts for 2 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane-trinitrile 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 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 fluoroethylene carbonate accounts for 1.5 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane trinitrile accounts for 0.2 percent of the total mass of the electrolyte0.5 percent of total mass percent of additive
Figure BDA0001529426030000061
Accounting for 0.5 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 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 fluoroethylene carbonate accounts for 1.0 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte
Figure BDA0001529426030000062
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 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 fluoroethylene carbonate accounts for 0.5 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte
Figure BDA0001529426030000063
Accounting for 1.5 percent of the total mass of the electrolyte.
Example 4
The non-aqueous organic solvent is ethylene carbonate or carbonic acidEthyl ester and methyl ethyl carbonate, which respectively account for 30 percent, 20 percent and 34 percent of the electrolyte by mass; 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 fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte
Figure BDA0001529426030000071
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 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 fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte
Figure BDA0001529426030000072
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 6
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 fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, and the additive 1, 3-propane sultone0.5 percent of additive biphenyl, 0.2 percent of additive 1,3, 6-hexanetricarbonitrile and 0.5 percent of additive
Figure BDA0001529426030000073
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 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 fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte
Figure BDA0001529426030000081
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 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 fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte
Figure BDA0001529426030000082
Accounts for the total mass of the electrolyteIs 1.0%.
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 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 fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte
Figure BDA0001529426030000083
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 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 fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte
Figure BDA0001529426030000091
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 34% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte, and the additive lithium difluoro oxalate borate accounts for0.3 percent of total mass of electrolyte, 1 percent of additive fluoroethylene carbonate, 0.5 percent of additive 1, 3-propane sultone, 0.2 percent of additive biphenyl, 0.5 percent of additive 1,3, 6-hexanetricarbonitrile and the like
Figure BDA0001529426030000092
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 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 fluoroethylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive 1, 3-propane sultone accounts for 0.5 percent of the total mass of the electrolyte, the additive biphenyl accounts for 0.2 percent of the total mass of the electrolyte, the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte, and the additive 1,3, 6-hexane trinitrile accounts for 0.5 percent of the total mass of the electrolyte
Figure BDA0001529426030000093
0.5 percent of additive accounting for the total mass of the electrolyte
Figure BDA0001529426030000094
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 12 were injected into the same batch of LiNi0.8Co0.15Al0.05O2In the 1Ah polymer soft package battery, the cycle life of the battery at normal temperature is 4.2V and 4.3V (table 1), the swelling degree and internal resistance change of the battery when the battery is placed at high temperature of 60 ℃ for 7 days are tested (table 2), and the overcharge test at 3C and 10V is tested (table 3), and the specific results are as follows:
TABLE 1
Normal temperature 500Z Retention ratio (4.2V) Normal temperature 300Z Retention Rate (4.3V)
Comparative example 1 74.41 60.37
Example 1 75.63 64.01
Example 2 78.88 67.54
Example 3 74.96 66.76
Example 4 75.25 65.92
Example 5 81.09 71.63
Example 6 80.46 71.22
Example 7 78.31 70.27
Example 8 77.50 69.86
Example 9 76.47 65.39
Example 10 78.97 67.54
Example 11 75.12 63.70
Example 12 81.56 72.84
TABLE 2
Figure BDA0001529426030000101
Figure BDA0001529426030000111
TABLE 3
3C, 10V test
Comparative example 1 Smoke-generating explosion
Example 1 Smoke-generating and non-explosion
Example 2 No smoke and explosion
Example 3 No smoke and explosion
Example 4 Smoke-generating and non-explosion
Example 5 No smoke and explosion
Example 6 No smoke and explosion
Example 7 No smoke and explosion
Example 8 No smoke and explosion
Example 9 No smoke and explosionFrying food
Example 10 No smoke and explosion
Example 11 Smoke-generating and non-explosion
Example 12 No smoke and explosion
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 terms of shelf life and safety performance both at normal temperature and at high temperature.
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 (8)

1. An electrolyte comprising a lithium salt, a non-aqueous solvent and an additive, characterized in that: the additive comprises one or more of an additive I and an additive III, and the structural general formula of the additive I is
Figure 882046DEST_PATH_IMAGE001
Wherein, R1 is phenyl alkyl acyl chloride or halogenated phenyl alkyl acyl chloride;
the general structural formula of the additive III is
Figure 268028DEST_PATH_IMAGE002
Wherein R6, R7 and R8 are independently hydrogen, hydroxyl, phenylalkanochloride or halogenated phenylalkanochloride, and at least one of R6, R7 and R8 is phenylalkanochloride orHalogenated phenyl alkyl acyl chloride, wherein n is an integer of 1-6;
the feeding mass of one or more of the additive I and the additive III accounts for 0.8-1.2% of the total mass of the electrolyte.
2. The electrolyte of claim 1, wherein: r1 is phenylformyl chloride, phenylacetyl chloride, phenylpropionyl chloride, phenylbutyryl chloride, halophenylformyl chloride, halophenylacetyl chloride, halophenylpropionyl chloride, or halophenylbutyryl chloride;
r6, R7 and R8 are independently hydrogen, hydroxyl, benzoyl chloride, phenylacetyl chloride, phenylpropionyl chloride, phenylbutyryl chloride, halophenyl formyl chloride, halophenyl acetyl chloride, halophenyl propionyl chloride or halophenyl butyryl chloride, at least one of R6, R7 and R8 is benzoyl chloride, phenylacetyl chloride, phenylpropionyl chloride, phenylbutyryl chloride, halophenyl formyl chloride, halophenyl acetyl chloride, halophenyl propionyl chloride or halophenyl butyryl chloride, and n is an integer of 1-3.
3. The electrolyte of claim 2, wherein: the additive I is
Figure 782186DEST_PATH_IMAGE003
Or
Figure 770870DEST_PATH_IMAGE004
(ii) a The additive III is
Figure 319663DEST_PATH_IMAGE005
。
4. The electrolyte of claim 1, wherein: the nonaqueous solvent is one or more selected from carbonate, carboxylate, ether and sulfone, and the feeding mass of the nonaqueous solvent accounts for 70-85% of the total amount of the electrolyte.
5. The method of claim 1An electrolyte, characterized in that: the lithium salt is selected from LiPF6、LiBF4、LiAsF6、LiClO4、LiBOB、LiDFOB、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N 、Li(CF3SO2)3C、Li(C6F5)4B、Li(C2F5SO2)2N 、LiBF3C2F5、LiPF3(C2F5)3The lithium salt is added into the electrolyte, wherein the mass of the lithium salt is 10-25% of the total mass of the electrolyte.
6. The electrolyte of claim 1, wherein: the additive also comprises other additives accounting for 0.5-5% of the total mass of the electrolyte, wherein the other additives are one or more selected from double-bond-containing cyclic carbonate, halogen-containing cyclic carbonate, an anhydride compound, sulfonate, sulfate, sulfite, a benzene compound, a nitrile compound, a cyclic ether compound, a phosphazene compound, phosphate, a boron compound, an amine compound and a silicon-containing compound.
7. A secondary lithium battery characterized in that: which employs the electrolyte of any one of claims 1 to 6.
8. A secondary lithium battery as claimed in claim 7, characterized in that: the positive active material of the secondary lithium battery is selected from LiNi0.5Mn1.5O4、LiNiPO4、LiCoPO4、Li3V2(PO4)3、LiNi1-xMnxO2、LiNi1-xCoxO2、LiNi1-y- zCoyMnzO2、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.
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