CN106711506A - Electrolyte containing styrene and derivative thereof and lithium secondary battery using electrolyte - Google Patents
Electrolyte containing styrene and derivative thereof and lithium secondary battery using electrolyte Download PDFInfo
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- CN106711506A CN106711506A CN201611195349.0A CN201611195349A CN106711506A CN 106711506 A CN106711506 A CN 106711506A CN 201611195349 A CN201611195349 A CN 201611195349A CN 106711506 A CN106711506 A CN 106711506A
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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
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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
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- 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
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Abstract
The invention belongs to the field of lithium secondary battery materials and discloses electrolyte containing styrene and a derivative thereof and a lithium secondary battery using the electrolyte. The electrolyte comprises an organic solvent, electrolyte lithium salt, styrene and a derivative and a functional additive thereof. A structural formula of styrene and the derivative thereof is as shown in formula (1), wherein R1, R2, R3, R4 and R5 are respectively independently hydrogen, halogen, C1-C20 alkyl or halogenated alkyl, C6-C26 aryl or halogenated aryl, C1-C4 nitrile groups, amino or alkoxy. Styrene and the derivative thereof are added into the electrolyte, and a stable passive film is formed on the surface of an electrode, so that the battery has low internal resistance while having good cycle performance. Formula (1).
Description
Technical field
The invention belongs to lithium secondary battery Material Field, and in particular to a kind of electrolyte containing Styrene and its derivatives and
Use the lithium secondary battery of the electrolyte.
Background technology
With the further broadening developed rapidly with range of application of lithium secondary battery technology, some key technologies need solution badly
Certainly, and electrolyte as battery important component, its effect can not underestimate.Additive is used as material important in electrolyte
Composition, its use can significantly improve the battery capacity of battery, rate charge-discharge performance, both positive and negative polarity matching performance, high/low temperature
Performance, cycle performance and security performance etc..
With the development of new-energy automobile, the combination property demand to battery proposes requirement higher, film for additive
Use be to improve one of lithium ion battery combination property effective way.At present in the battery, the oxidation Decomposition deterioration of electrolyte
Battery performance, and the dissolution of metal ion is frequently accompanied by during circulation and high temperature storage, cause battery performance serious
Decline.
Research shows, performance of lithium ion battery can be effectively improved by the interfacial property for improving electrode and electrolyte.Fluorine
There is preferable film forming characteristics for ethylene carbonate, vinylene carbonate, sulfonate compound and nitrile compounds etc., it is general at present
All over being applied in lithium-ion battery electrolytes.As patent of invention CN105140562A derives by addition benzene dinitrile in electrolyte
Thing improves circulating battery and high-temperature behavior, reduces flatulence.WO01/03229A changes fluorobenzene derivatives as electrolysis additive
Kind cycle performance of battery.However, the species of lithium secondary battery film for additive is still less at present, function is also more single.Therefore
The new film for additive of exploitation is significant.
The content of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the invention is to provide a kind of containing benzene
The electrolyte of ethene and its derivative.
Preparation method another object of the present invention is to provide the above-mentioned electrolyte containing Styrene and its derivatives.
It is still another object of the present invention to provide a kind of lithium secondary battery using above-mentioned electrolyte.
The object of the invention is achieved through the following technical solutions：
A kind of electrolyte containing Styrene and its derivatives, including organic solvent, electrolyte lithium salt, styrene and its derivative
Thing and functional additive, shown in the structural formula such as formula (1) of the Styrene and its derivatives：
Wherein R1, R2, R3, R4, R5It is independently each hydrogen, halogen, C1~C20 alkyl or haloalkyl, C6~C26 aryl
Or halogenated aryl, C1~C4 itrile groups, amino or alkoxy.
Preferably, the addition of the Styrene and its derivatives is organic solvent and electrolyte lithium salt gross weight
0.1%~10%.
Preferably, the organic solvent include ethylene carbonate, propene carbonate, diethyl carbonate, methyl ethyl carbonate,
At least two mixing in ethyl acetate, propyl acetate.
Preferably, the electrolyte lithium salt is lithium hexafluoro phosphate；Electrolyte lithium salt concentration in organic solvent
It is 0.8~1.5mol/L.
Preferably, the other functions additive is vinylene carbonate, vinylethylene carbonate, fluoro ethylene carbonate
At least one in ester, PS；The addition of the other functions additive is organic solvent and electrolyte lithium
The 0.5%~10% of salt gross weight.
The preparation method of the above-mentioned electrolyte containing Styrene and its derivatives, comprises the following steps：
(1) by organic solvent purifying removal of impurities, water removal；
(2) at ambient temperature, in electrolyte lithium salt being added into step (1) gained organic solvent, and stir；
(3) Styrene and its derivatives and other functional additives are added, and are stirred, obtain it is described containing styrene and
The electrolyte of its derivative.
Clarification described in step (1), water removal are preferably by molecular sieve, activated carbon, calcium hydride, lithium hydride, anhydrous
Any one or a few in calcium oxide, calcium chloride, phosphorus pentoxide, alkali metal or alkaline-earth metal is processed.
A kind of lithium secondary battery using above-mentioned electrolyte, the lithium secondary battery includes lithium ion battery, lithium-sulfur cell
Or lithium-air battery.
The lithium ion battery includes positive plate, negative plate, barrier film and the electrolysis containing Styrene and its derivatives
Liquid；The positive plate includes the positive electrode active materials of embedded or deintercalate lithium ions, conductive agent, collector and by positive-active material
The bonding agent that material and conductive agent are combined with the collector；The negative plate includes being embedded in or the negative pole of deintercalate lithium ions is lived
Property material, conductive agent, collector and the bonding agent that negative active core-shell material and conductive agent are combined with the collector.
The positive electrode active materials refer to lithium-containing transition metal oxide, and described lithium-containing transition metal oxide is Li1+a
(NixCoyMn1-x-y)O2(0≤a≤0.3,0≤x≤1,0≤y≤1), Li (NinMnmCo2-n-m)O4, (0≤n≤2,0≤m≤
2)、LiMp(PO4)qAt least one of (M is Fe, Ni, Co, Mn, V, the ＜ q ＜ 5 of 0 ＜ p ＜ 5,0)；The negative active core-shell material includes
At least one in lithium metal, lithium alloy, carbon material, silicon or tin and its oxide.
Relative to prior art, the invention has the advantages that and beneficial effect：
The present invention forms the interfacial film of stabilization by adding Styrene and its derivatives in the electrolytic solution in electrode surface,
Improve interfacial property.Battery is embodied in while with good circulation performance, relatively low internal resistance is embodied.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
A kind of lithium secondary cell electrolyte, consists predominantly of machine solvent, electrolyte lithium salt and additive, and additive includes work(
Can additive and Styrene and its derivatives.The organic solvent be ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and
The mass ratio of methyl ethyl carbonate is 1:2.Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 0.8mol/L.
The functional additive is vinylene carbonate and fluorinated ethylene carbonate, respectively 1.0% He of electrolyte gross mass
2.0%.The Styrene and its derivatives are styrene (I), are the 1.0% of electrolyte gross mass.
The preparation method of the present embodiment electrolyte, comprises the following steps：
(1) organic solvent warpType molecular sieve, calcium hydride, lithium hydride clarification, water removal；
(2) at ambient temperature, in electrolyte lithium salt being added into step (1) gained organic solvent, and stir；
(3) functional additive and Styrene and its derivatives are added, and is stirred, obtain described containing styrene and its spreading out
Biological electrolyte.
The present embodiment electrolyte containing Styrene and its derivatives is used for LiNi0.5Co0.2Mn0.3O2/ graphite flexible packaged battery
Pond, tests LiNi0.5Co0.2Mn0.3O2/ graphite flexible-packed battery 3.0~4.35V under normal temperature environment, 1C rate charge-discharges are followed
Ring performance and 60 DEG C of 14 days high temperature storages.
Embodiment 2
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate and methyl ethyl carbonate, and the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:3.It is described
Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.0mol/L.The functional additive is vinylene carbonate
With 1,3- propane sultones, respectively the 2.0% of electrolyte gross mass and 1.0%.The Styrene and its derivatives are benzene
Ethene, is the 3.0% of electrolyte gross mass.Thus prepared electrolyte is applied to according to method same as Example 1
LiNi0.8Co0.15Al0.05O2/ graphite flexible-packed battery, tests LiNi0.8Co0.15Al0.05O2Graphite flexible-packed battery is in normal temperature ring
The cycle performance of 3.0~4.2V under border, 1C rate charge-discharge and 60 DEG C of 14 days high temperature storages.
Embodiment 3
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate and diethyl carbonate, and the mass ratio of ethylene carbonate and diethyl carbonate is 1:2.It is described
Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.0mol/L.The functional additive is vinylene carbonate
And fluorinated ethylene carbonate, respectively the 1.0% of electrolyte gross mass and 3.0%.The Styrene and its derivatives are 2,6-
Difluoro styrene (II), is the 0.5% of electrolyte gross mass.By thus prepared electrolyte according to side same as Example 1
Method is applied to LiNi0.5Co0.2Mn0.3O2/ graphite flexible-packed battery, tests LiNi0.5Co0.2Mn0.3O2Graphite flexible-packed battery is normal
The cycle performance of 3.0~4.35V under warm environment, 1C rate charge-discharge and 60 DEG C of 14 days high temperature storages.
Embodiment 4
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate and diethyl carbonate, and the mass ratio of ethylene carbonate and diethyl carbonate is 1:3.It is described
Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.0mol/L.The functional additive is vinylene carbonate
1.0%, 2.0% and the 2.0% of ester, 1,3- propane sultones and fluorinated ethylene carbonate, respectively electrolyte gross mass.Institute
Styrene and its derivatives are stated for 2,6- difluoro styrene, is the 3.0% of electrolyte gross mass.Thus prepared electrolyte is pressed
LiNi is applied to according to method same as Example 10.6Co0.2Mn0.2O2/ silicon-carbon flexible-packed battery, test
LiNi0.6Co0.2Mn0.2O2Silicon-carbon flexible-packed battery 3.0~4.2V under normal temperature environment, the cycle performance of 1C rate charge-discharges and
60 DEG C of 14 days high temperature storages.
Embodiment 5
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, ethylene carbonate, diethyl carbonate and acetic acid second
The mass ratio of ester is 1:2:1.Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.2mol/L.The work(
Energy additive is vinylene carbonate and fluorinated ethylene carbonate, respectively the 0.5% of electrolyte gross mass and 5.0%.It is described
The pentafluorostyrene (III) of Styrene and its derivatives 2,3,4,5,6-, is the 1.0% of electrolyte gross mass.By thus prepared electricity
Solution liquid is applied to LiCoO according to method same as Example 12/ silicon-carbon flexible-packed battery, tests LiCoO2Silicon-carbon flexible packaged battery
Pond 3.0~4.4V under normal temperature environment, the cycle performance of 1C rate charge-discharges and 60 DEG C of 14 days high temperature storages.
Embodiment 6
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, ethylene carbonate, diethyl carbonate and acetic acid second
The mass ratio of ester is 1:1:1.Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.0mol/L.The work(
Energy additive is 1,3- propane sultones and fluorinated ethylene carbonate, respectively the 1.0% of electrolyte gross mass and 4.0%.
The Styrene and its derivatives are 2,3,4,5,6- pentafluorostyrenes, are the 5.0% of electrolyte gross mass.Will be thus prepared
Electrolyte is applied to LiCoO according to method same as Example 12/ silicon-carbon flexible-packed battery, tests LiCoO2Silicon-carbon flexible package
Battery 3.0~4.4V under normal temperature environment, the cycle performance of 1C rate charge-discharges and 60 DEG C of 14 days high temperature storages.
Embodiment 7
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, ethylene carbonate, diethyl carbonate and carbonic acid first
The mass ratio of ethyl ester is 1:1:2.Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.5mol/L.It is described
Functional additive is vinylethylene carbonate and fluorinated ethylene carbonate, respectively the 1.0% of electrolyte gross mass and 2.0%.
The Styrene and its derivatives are 3- methyl styrenes (IV), are the 1.0% of electrolyte gross mass.By thus prepared electrolysis
Liquid is applied to LiCoO according to method same as Example 12/ graphite flexible-packed battery, tests LiCoO2Graphite flexible-packed battery
The cycle performance of 3.0~4.4V under normal temperature environment, 1C rate charge-discharge and 60 DEG C of 14 days high temperature storages.
Embodiment 8
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate, propene carbonate and methyl ethyl carbonate, ethylene carbonate, propene carbonate and carbonic acid first
The mass ratio of ethyl ester is 4:1:5.Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 0.8mol/L.It is described
Functional additive is fluorinated ethylene carbonate, is the 3.0% of electrolyte gross mass.The Styrene and its derivatives are 3- methyl
Styrene, is the 3.0% of electrolyte gross mass.Thus prepared electrolyte is applied to according to method same as Example 1
LiCoO2/ graphite flexible-packed battery, tests LiCoO2Graphite flexible-packed battery 3.0~4.4V under normal temperature environment, 1C multiplying power charge and discharge
The cycle performance and 60 DEG C of 14 days high temperature storages of electricity.
Embodiment 9
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate, propene carbonate and diethyl carbonate, ethylene carbonate, propene carbonate and carbonic acid two
The mass ratio of ethyl ester is 4:1:5.Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.2mol/L.It is described
Functional additive is vinylene carbonate, vinylethylene carbonate and fluorinated ethylene carbonate, respectively electrolyte gross mass
1.0%th, 1.0% and 3.0%.The Styrene and its derivatives are 2 (trifluoromethyl) styrene (V), are electrolyte gross mass
1.0%.Thus prepared electrolyte is applied to LiNi according to method same as Example 10.8Co0.1Mn0.1O2/ graphite
Flexible-packed battery, tests LiNi0.8Co0.1Mn0.1O2Graphite flexible-packed battery 3.0~4.2V under normal temperature environment, 1C multiplying power charge and discharge
The cycle performance and 60 DEG C of 14 days high temperature storages of electricity.
Embodiment 10
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate and diethyl carbonate, and the mass ratio of ethylene carbonate and diethyl carbonate is 1:1.It is described
Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.0mol/L.The functional additive is vinylene carbonate
1.0%, 1.0% and the 3.0% of ester, 1,3- propane sultones and fluorinated ethylene carbonate, respectively electrolyte gross mass.Institute
Styrene and its derivatives are stated for 2 (trifluoromethyl) styrene, is the 3.0% of electrolyte gross mass.By thus prepared electrolysis
Liquid is applied to LiNi according to method same as Example 10.8Co0.1Mn0.1O2/ graphite flexible-packed battery, test
LiNi0.8Co0.15Al0.05O2Graphite flexible-packed battery 3.0~4.2V under normal temperature environment, the cycle performance of 1C rate charge-discharges and
60 DEG C of 14 days high temperature storages.
Embodiment 11
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate and methyl ethyl carbonate, and the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.It is described
Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 0.8mol/L.The functional additive is vinylene carbonate
Ester, is the 1.0% of electrolyte gross mass.The Styrene and its derivatives are 4- cyclohexylstyrenes (VI), are total electrolyte
The 0.5% of quality.Thus prepared electrolyte is applied to LiNi according to method same as Example 11/3Co1/3Mn1/3O2/
Silicon-carbon flexible-packed battery, tests LiNi1/3Co1/3Mn1/3O2Silicon-carbon flexible-packed battery 3.0~4.4V under normal temperature environment, 1C multiplying powers
The cycle performance of discharge and recharge and 60 DEG C of 14 days high temperature storages.
Embodiment 12
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate and diethyl carbonate, and the mass ratio of ethylene carbonate and diethyl carbonate is 1:2.It is described
Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 0.8mol/L.The functional additive is fluoro ethylene carbonate
Ester, is the 3.0% of electrolyte gross mass.The Styrene and its derivatives are 4- cyclohexylstyrenes, are electrolyte gross mass
3.0%.Thus prepared electrolyte is applied to LiNi according to method same as Example 10.6Co0.2Mn0.2O2/ graphite
Flexible-packed battery, tests LiNi0.6Co0.2Mn0.2O2Graphite flexible-packed battery 3.0~4.2V under normal temperature environment, 1C multiplying power charge and discharge
The cycle performance and 60 DEG C of 14 days high temperature storages of electricity.
Embodiment 13
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate and methyl ethyl carbonate, and the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.It is described
Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.2mol/L.The functional additive is vinylene carbonate
2.0%, 2.0% and the 2.0% of ester, 1,3- propane sultones and fluorinated ethylene carbonate, respectively electrolyte gross mass.Institute
Styrene and its derivatives are stated for 4- vinyl biphenyls (VII), is the 0.1% of electrolyte gross mass.By thus prepared electrolyte
LiNi is applied to according to method same as Example 10.5Co0.2Mn0.3O2/ graphite flexible-packed battery, test
LiNi0.5Co0.2Mn0.3O2Graphite flexible-packed battery 3.0~4.35V under normal temperature environment, the cycle performance of 1C rate charge-discharges and
60 DEG C of 14 days high temperature storages.
Embodiment 14
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate and diethyl carbonate, and the mass ratio of ethylene carbonate and diethyl carbonate is 1:1.It is described
Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.2mol/L.The functional additive is vinylene carbonate
With 1,3- propane sultones, respectively the 3.0% of electrolyte gross mass and 2.0%.The Styrene and its derivatives are 4-
Vinyl biphenyl, is the 4.0% of electrolyte gross mass.Should according to method same as Example 1 by thus prepared electrolyte
For LiNi0.8Co0.1Mn0.1O2/ graphite flexible-packed battery, tests LiNi0.8Co0.1Mn0.1O2Graphite flexible-packed battery is in normal temperature ring
The cycle performance of 3.0~4.2V under border, 1C rate charge-discharge and 60 DEG C of 14 days high temperature storages.
Embodiment 15
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, ethylene carbonate, diethyl carbonate and carbonic acid first
The mass ratio of ethyl ester is 2:5:3.Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.0mol/L.It is described
Functional additive is 1,3- propane sultones and fluorinated ethylene carbonate, respectively 2.0% He of electrolyte gross mass
2.0%.The Styrene and its derivatives are 4- cyanostyrenes (VIII), are the 2.0% of electrolyte gross mass.Will be thus prepared
Electrolyte be applied to LiNi according to method same as Example 10.5Co0.2Mn0.3O2/ graphite flexible-packed battery, test
LiNi0.5Co0.2Mn0.3O2Graphite flexible-packed battery 3.0~4.35V under normal temperature environment, the cycle performance of 1C rate charge-discharges and
60 DEG C of 14 days high temperature storages.
Embodiment 16
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, ethylene carbonate, diethyl carbonate and carbonic acid first
The mass ratio of ethyl ester is 1:2:1.Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.5mol/L.It is described
Functional additive is 1,3- propane sultones and vinylethylene carbonate, respectively 2.0% He of electrolyte gross mass
1.0%.The Styrene and its derivatives are 4- cyanostyrenes, are the 5.0% of electrolyte gross mass.By thus prepared electricity
Solution liquid is applied to LiNi according to method same as Example 10.6Co0.2Mn0.2O2/ graphite flexible-packed battery, test
LiNi0.6Co0.2Mn0.2O2Graphite flexible-packed battery 3.0~4.2V under normal temperature environment, the cycle performance of 1C rate charge-discharges and
60 DEG C of 14 days high temperature storages.
Embodiment 17
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate, propene carbonate and methyl ethyl carbonate, ethylene carbonate, propyl acetate and methyl ethyl carbonate
The mass ratio of ester is 3:2:5.Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 0.8mol/L.The work(
Energy additive is 1,3- propane sultones and fluorinated ethylene carbonate, respectively the 3.0% of electrolyte gross mass and 2.0%.
The Styrene and its derivatives are 2- aminostyryls (Ⅸ), are the 1.0% of electrolyte gross mass.By thus prepared electrolysis
Liquid is applied to LiCoO according to method same as Example 12/ silicon-carbon flexible-packed battery, tests LiCoO2Silicon-carbon flexible-packed battery
The cycle performance of 3.0~4.4V under normal temperature environment, 1C rate charge-discharge and 60 DEG C of 14 days high temperature storages.
Embodiment 18
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate, propene carbonate and diethyl carbonate, ethylene carbonate, propyl acetate and carbonic acid diethyl
The mass ratio of ester is 3:2:5.Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.2mol/L.The work(
Energy additive is that vinylene carbonate and fluorinated ethylene carbonate are respectively the 3.0% and 2.0% of electrolyte gross mass.The benzene
Ethene and its derivative are 2- aminostyryls, are the 3.0% of electrolyte gross mass.By thus prepared electrolyte according to reality
Apply the identical method of example 1 and be applied to LiCoO2/ silicon-carbon flexible-packed battery, tests LiCoO2Silicon-carbon flexible-packed battery is in normal temperature environment
Lower 3.0~4.4V, the cycle performance of 1C rate charge-discharges and 60 DEG C of 14 days high temperature storages.
Embodiment 19
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate and diethyl carbonate, and the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.It is described
Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.2mol/L.The functional additive is vinylene carbonate
1.0%, 3.0% and the 2.0% of ester, 1,3- propane sultones and fluorinated ethylene carbonate, respectively electrolyte gross mass.Institute
Styrene and its derivatives are stated for 3,4- dimethoxy styrenes (Ⅹ), is the 0.1% of electrolyte gross mass.Will be thus prepared
Electrolyte is applied to LiNi according to method same as Example 10.5Co0.2Mn0.3O2/ silicon-carbon flexible-packed battery, test
LiNi0.5Co0.2Mn0.3O2Silicon-carbon flexible-packed battery 3.0~4.35V under normal temperature environment, the cycle performance of 1C rate charge-discharges and
60 DEG C of 14 days high temperature storages.
Embodiment 20
The preparation method containing Styrene and its derivatives electrolyte of the present embodiment is same as Example 1, except that,
The organic solvent is ethylene carbonate and diethyl carbonate, and the mass ratio of ethylene carbonate and diethyl carbonate is 1:1.It is described
Electrolyte lithium salt lithium hexafluoro phosphate concentration in organic solvent is 1.5mol/L.The functional additive is vinylene carbonate
With 1,3- propane sultones, respectively the 3.0% of electrolyte gross mass and 2.0%.The Styrene and its derivatives are 3,
4- dimethoxy styrenes, are the 5.0% of electrolyte gross mass.By thus prepared electrolyte according to same as Example 1
Method is applied to LiNi0.8Co0.15Al0.05O2/ graphite flexible-packed battery, tests LiNi0.8Co0.15Al0.05O2Graphite flexible packaged battery
Pond 3.0~4.2V under normal temperature environment, the cycle performance of 1C rate charge-discharges and 60 DEG C of 14 days high temperature storages.
Comparative example 1
The preparation method of the electrolyte of this comparative example is same as Example 1, except that, it is added without styrene and its spreads out
Biology, thus prepared electrolyte is applied to according to method same as Example 1 to test its performance in full battery.
Comparative example 2
The preparation method of the electrolyte of this comparative example is same as Example 3, except that, it is added without 2,6- difluorobenzene second
Alkene additive, thus prepared electrolyte is applied to according to method same as Example 3 to test its performance in full battery.
Comparative example 3
The preparation method of the electrolyte of this comparative example is same as Example 5, except that, it is added without 2,3,4,5,6- five
Fluorobenzene ethene additive, thus prepared electrolyte is applied to according to method same as Example 5 to test it in full battery
Performance.
Comparative example 4
The preparation method of the electrolyte of this comparative example is same as Example 7, except that, it is added without 3- methyl styrenes
Additive, thus prepared electrolyte is applied to according to method same as Example 7 to test its performance in full battery.
Comparative example 5
The preparation method of the electrolyte of this comparative example is same as Example 9, except that, it is added without 2 (trifluoromethyls)
Styrene additive, thus prepared electrolyte is applied to according to method same as Example 9 to test its property in full battery
Energy.
Comparative example 6
The preparation method of the electrolyte of this comparative example is identical with embodiment 11, except that, it is added without 4- cyclohexyl benzenes
Ethene additive, thus prepared electrolyte is applied to test its property in full battery according to the identical method of embodiment 11
Energy.
Comparative example 7
The preparation method of the electrolyte of this comparative example is identical with embodiment 13, except that, it is added without 4- vinyl connection
Benzene additive, thus prepared electrolyte is applied to test its performance in full battery according to the identical method of embodiment 13.
Comparative example 8
The preparation method of the electrolyte of this comparative example is identical with embodiment 15, except that, it is added without 4- itrile group benzene second
Alkene additive, thus prepared electrolyte is applied to test its performance in full battery according to the identical method of embodiment 15.
Comparative example 9
The preparation method of the electrolyte of this comparative example is identical with embodiment 17, except that, it is added without 2- aminobenzene second
Alkene additive, thus prepared electrolyte is applied to test its performance in full battery according to the identical method of embodiment 17.
Comparative example 10
The preparation method of the electrolyte of this comparative example is identical with embodiment 19, except that, it is added without 3,4- dimethoxies
Base styrene additive, thus prepared electrolyte is applied to test it in full battery according to the identical method of embodiment 19
Performance.
The application experiment of embodiment and comparative example：
Circulation experiment：By comparative example 1~10 and the gained battery of embodiment 1~20 at 25 DEG C of room temperature with the discharge and recharge of 1C times
Rate carries out charge and discharge cycles test, the 300th time and the 500th cyclic discharge capacity is recorded respectively and is circulated and must be put divided by the 1st time
Capacitance obtains final product capability retention, records result such as table 1.
High temperature storage is tested：By at 25 DEG C of comparative example 1~10 and 1~20 gained battery room temperature of embodiment with the discharge and recharge of 1C
Multiplying power carries out 5 charge and discharge cycles tests, and then 1C multiplying powers are charged to full power state.1C capacity and the internal resistance of cell are recorded respectively.Will
Full power state battery is stored 14 days at 60 DEG C, records the internal resistance of cell and 1C discharge capacities, is respectively obtained battery high-temperature storage and is held
The experimental datas such as amount conservation rate, capacity response rate, internal resistance rate of change, record result such as table 1.
High temperature storage internal resistance of cell rate of change calculation is following formula：
Wherein, T is the internal resistance of cell of high temperature storage thousand, T0It is the internal resistance of cell after high temperature storage.Lithium secondary battery is tested
Partial results are referring to table 1.
In addition to following table parameter, other specification and preparation method are with embodiment 1.
The specific chemical formula correspondence of phenylethylene additive used in above-described embodiment is as follows：
Above example and comparative example gained battery performance test effect compare：
The test result of the embodiment of table 1 and comparative example
Styrene and its derivatives are can be seen that to capacitance of lithium secondary battery conservation rate and high temperature storage by the data of table 1
There is improvement, the present invention has prominent advantage, is mainly manifested in electricity using Styrene and its derivatives as electrolysis additive
Internal resistance of cell rate of change after the circulation volume conservation rate and high temperature storage in pond.Embodiment 1-20 is substantially better than its comparative example, addition
The electrolyte of Styrene and its derivatives can effectively extend battery life and reduce the change of internal resistance under the internal resistance of cell and high temperature
Rate.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of electrolyte containing Styrene and its derivatives, it is characterised in that：The electrolyte includes organic solvent, electrolyte
Lithium salts, Styrene and its derivatives and functional additive, shown in the structural formula such as formula (1) of the Styrene and its derivatives：
Wherein R1, R2, R3, R4, R5It is independently each hydrogen, halogen, C1~C20 alkyl or haloalkyl, C6~C26 aryl or halogen
For aryl, C1~C4 cyano group, amino or alkoxy.
2. a kind of electrolyte containing Styrene and its derivatives according to claim 1, it is characterised in that：The styrene
And its 0.1%~10% that the addition of derivative is organic solvent and electrolyte lithium salt gross weight.
3. the electrolyte of a kind of Styrene and its derivatives according to claim 1, it is characterised in that：The organic solvent
Including in ethylene carbonate, propene carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate, propyl acetate at least two
Mixing.
4. a kind of electrolyte containing Styrene and its derivatives according to claim 1, it is characterised in that：The electrolyte
Lithium salts is lithium hexafluoro phosphate；Electrolyte lithium salt concentration in organic solvent is 0.8~1.5mol/L.
5. a kind of electrolyte containing Styrene and its derivatives according to claim 1, it is characterised in that：Described other work(
Energy additive is at least in vinylene carbonate, vinylethylene carbonate, fluorinated ethylene carbonate, PS
Kind；The addition of the other functions additive is the 0.5%~10% of organic solvent and electrolyte lithium salt gross weight.
6. a kind of preparation method of the electrolyte containing Styrene and its derivatives described in any one of Claims 1 to 5, its feature
It is to comprise the following steps：
(1) by organic solvent purifying removal of impurities, water removal；
(2) at ambient temperature, in electrolyte lithium salt being added into step (1) gained organic solvent, and stir；
(3) Styrene and its derivatives and other functions additive are added, and is stirred, obtain described containing styrene and its spreading out
Biological electrolyte.
7. the preparation method of a kind of electrolyte containing Styrene and its derivatives according to claim 6, it is characterised in that：
Clarification, water removal described in step (1) refer to by molecular sieve, activated carbon, calcium hydride, lithium hydride, anhydrous calcium oxide, chlorine
Any one or a few in change calcium, phosphorus pentoxide, alkali metal or alkaline-earth metal is processed.
8. the lithium secondary battery of the electrolyte of Styrene and its derivatives is contained described in a kind of 1~5 any one of usage right requirement, its
It is characterised by：The lithium secondary battery includes lithium ion battery, lithium-sulfur cell or lithium-air battery.
9. a kind of lithium secondary battery according to claim 8, it is characterised in that：The lithium ion battery include positive plate,
Electrolyte containing Styrene and its derivatives described in negative plate, barrier film and any one of Claims 1 to 5；The positive plate bag
Include the positive electrode active materials of embedded or deintercalate lithium ions, conductive agent, collector and by positive electrode active materials and conductive agent and institute
State the bonding agent of collector combination；The negative plate includes being embedded in or the negative active core-shell material of deintercalate lithium ions, conductive agent,
Collector and the bonding agent that negative active core-shell material and conductive agent are combined with the collector.
10. a kind of lithium secondary battery according to claim 9, it is characterised in that：The positive electrode active materials refer to containing lithium
Transition metal oxide, described lithium-containing transition metal oxide is that described lithium-containing transition metal oxide is Li1+a
(NixCoyMn1-x-y)O2、Li(NinMnmCo2-n-m)O4、LiMp(PO4)qAt least one, wherein 0≤a≤0.3,0≤x≤1,0
≤ y≤1,0≤n≤2,0≤m≤2, M is Fe, Ni, Co, Mn or V, the ＜ q ＜ 5 of 0 ＜ p ＜ 5,0；The negative active core-shell material includes
At least one in lithium metal, lithium alloy, carbon material, silicon or tin and its oxide.
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Application publication date: 20170524 |