CN105680096A - Electrolyte and lithium ion battery containing same - Google Patents

Electrolyte and lithium ion battery containing same Download PDF

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CN105680096A
CN105680096A CN201610017727.XA CN201610017727A CN105680096A CN 105680096 A CN105680096 A CN 105680096A CN 201610017727 A CN201610017727 A CN 201610017727A CN 105680096 A CN105680096 A CN 105680096A
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carbon number
heterocyclic ring
halogen atom
electrolyte
lithium
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CN105680096B (en
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王耀辉
史松君
谢岚
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Dongguan Amperex Technology 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

Abstract

The application relates to an electrolyte and a lithium ion battery containing the same. The electrolyte comprises an organic solvent, a lithium salt and an additive, wherein the additive comprises nitrogen-containing heterocyclic ring-boron trifluoride coordination compound and a silica phosphatide compound, and the nitrogen-containing heterocyclic ring is selected from at least one of heterocyclic ring containing pyridyl, heterocyclic ring containing pyridazine, heterocyclic ring containing pyrimidyl, heterocyclic ring containing pyrazinyl, heterocyclic ring containing pyrryl, heterocyclic ring containing pyrazolyl and heterocyclic ring containing imidazolyl. In the electrolyte provided by the application, the nitrogen-containing heterocyclic ring-boron trifluoride coordination compound and the silica phosphatide compound are simultaneously contained, and thus, the cycle performance of the lithium ion battery in a normal temperature and a high temperature can be improved.

Description

Electrolyte and include the lithium ion battery of this electrolyte
Technical field
The application relates to field of lithium, particularly relates to a kind of electrolyte and includes the lithium ion battery of this electrolyte.
Background technology
At present, the positive electrode active materials adopted in lithium ion battery mainly has LiMn2O4, cobalt acid lithium, ternary material, LiFePO 4 etc., under normal conditions, select the charge cutoff voltage of lithium ion battery of the above-mentioned positive electrode being previously mentioned less than 4.2V, but it is as the progress of science and technology and the development in market, the energy density promoting lithium ion battery seems important and urgent day by day, and the effective ways of a kind of energy density promoting lithium ion battery are to develop high-voltage lithium ion batteries.
But, such as under the high voltage of 4.6V, causing the electrolyte positive electrode surface oxidation Decomposition at battery of routine, the oxidation Decomposition of electrolyte self can promote the deteriorative reaction of positive electrode active materials simultaneously, affect the performance of lithium ion battery further, for instance cycle performance.
Summary of the invention
In order to solve the problems referred to above, the applicant has carried out studying with keen determination, found that: when electrolyte includes nitrogen heterocyclic ring-boron trifluoride coordination compound and silica phosphoric ester compound simultaneously, using the teaching of the invention it is possible to provide the cycle performance at ambient and elevated temperatures of lithium ion battery, thus completing the application.
The purpose of the application is in that to provide a kind of electrolyte, including organic solvent, lithium salts and additive, described additive includes nitrogen heterocyclic ring-boron trifluoride coordination compound and silica phosphoric ester compound, wherein, described nitrogen heterocyclic ring is at least one in the heterocycle containing pyridine radicals, the heterocycle containing pyridazinyl, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, heterocycle containing pyrrole radicals, the heterocycle of pyrazolyl containing and the heterocycle containing imidazole radicals.
The another object of the application is in that to provide a kind of lithium ion battery, including the positive plate containing positive electrode active materials, containing the negative plate of negative active core-shell material, isolating membrane and electrolyte provided herein.
In the electrolyte that the application provides, owing to including nitrogen heterocyclic ring-boron trifluoride coordination compound mentioned above and silica phosphoric ester compound simultaneously, therefore, it is possible to improve lithium ion battery cycle performance at ambient and elevated temperatures.
Detailed description of the invention
Being described in detail below by the application, the feature of the application and advantage will illustrate along with these and become more apparent from, clearly.
The purpose of the application is in that to provide a kind of electrolyte, including organic solvent, lithium salts and additive, described additive includes nitrogen heterocyclic ring-boron trifluoride coordination compound and silica phosphoric ester compound, wherein, described nitrogen heterocyclic ring is at least one in the heterocycle containing pyridine radicals, the heterocycle containing pyridazinyl, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, heterocycle containing pyrrole radicals, the heterocycle of pyrazolyl containing and the heterocycle containing imidazole radicals.
In above-mentioned electrolyte, in described " heterocycle containing pyridine radicals, the heterocycle containing pyridazinyl, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, heterocycle containing pyrrole radicals, the heterocycle of pyrazolyl containing, heterocycle containing imidazole radicals ", pyridine radicals, pyridazinyl, pyrimidine radicals, pyrazinyl, pyrrole radicals, pyrazolyl, imidazole radicals all can be replaced by other groups, for instance can be replaced by substituent groups such as halogen atom, hydrogen atom, alkyl.
In above-mentioned electrolyte, described nitrogen heterocyclic ring-boron trifluoride coordination compound refers to the nitrogen heterocyclic ring organic molecule of above-mentioned raising and the coordination compound of boron trifluoride formation, boron trifluoride is anion, and nitrogen heterocyclic ring is cation, and whole azacyclo--boron trifluoride coordination compound is electric neutrality.
Preferably, described nitrogen heterocyclic ring-boron trifluoride coordination compound is at least one in the compound shown in following formula I, Formula II, formula III, Formulas I V, Formula V, Formula IV and Formula VII:
In above-mentioned Formulas I, Formula II, formula III, Formulas I V, Formula V, Formula IV and Formula VII, R11、R12、R13、R14、R15、R21、R22、R23、R24、R31、R32、R33、R34、R41、R42、R43、R44、R51、R52、R53、R54、R61、R62、R63、R71、R72、R73It is each independently selected from hydrogen atom, halogen atom, carbon number is the alkyl of 1～20, carbon number is the thiazolinyl of 2～20, carbon number is the aryl of 6～26, carbon number is the alkoxyl of 1～20, carbon number is the aryloxy group of 6～26, and above-mentioned carbon number is the alkyl of 1～20, carbon number is the thiazolinyl of 2～20, carbon number is the aryl of 6～26, carbon number is the alkoxyl of 1～20, carbon number is that the aryloxy group of 6～26 is by halogen atom, sulfonic group or sulfonyl replace the one in the group formed, wherein, halogen atom is F, Cl, Br, preferred F, Cl. it addition, alkyl mentioned above, thiazolinyl, aryl also can be replaced by the group of the group containing pyridine radicals or thienyl-containing.
In above-mentioned Formulas I, Formula II, formula III, Formulas I V, Formula V, Formula IV and Formula VII, substituent group is as described below.
Carbon number is the alkyl of 1～20, and alkyl can be chain-like alkyl, it is possible to for cycloalkyl, the ring hydrogen being positioned at cycloalkyl can be replaced by alkyl, and in described alkyl, the preferred lower limit of carbon number is 2,3,4,5, it is preferred that higher limit is 3,4,5,6,8,10,12,14,16,18. Preferably, selecting carbon number is the alkyl of 1～10, further preferably, selecting carbon number is the chain-like alkyl of 1～6, and carbon number is the cycloalkyl of 3～8, still more preferably, selecting carbon number is the chain-like alkyl of 1～4, and carbon number is the cycloalkyl of 5～7. As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, cyclopenta, cyclohexyl.
Carbon number is the thiazolinyl of 2～20, can be cyclic alkenyl radical, it is possible to for chain thiazolinyl. It addition, the number of double bond is preferably 1 in thiazolinyl. In described thiazolinyl, the preferred lower limit of carbon number is 3,4,5, it is preferred that higher limit is 3,4,5,6,8,10,12,14,16,18.Preferably, selecting carbon number is the thiazolinyl of 2～10, it is further preferred that selecting carbon number is the thiazolinyl of 2～6, it is further preferred that selecting carbon number is the thiazolinyl of 2～5. As the example of thiazolinyl, specifically can enumerate: vinyl, pi-allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.
Carbon number is the aryl of 6～26, for instance phenyl, benzene alkyl, at least contain the aryl such as xenyl of a phenyl, condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, and xenyl and condensed-nuclei aromatics base also can be replaced by alkyl or thiazolinyl. Preferably, selecting carbon number is the aryl of 6～16, it is further preferred that selecting carbon number is the aryl of 6～14, it is further preferred that selecting carbon number is the aryl of 6～9. As the example of aryl, specifically can enumerate: phenyl, benzyl, xenyl, p-methylphenyl, o-tolyl, a tolyl.
When in the alkyl that the aforementioned carbon number being previously mentioned is 1～20 containing oxygen atom, alkoxyl can be formed. Preferably, selecting carbon number is the alkoxyl of 1～10, it is further preferred that selecting carbon number is the alkoxyl of 1～6, it is further preferred that selecting carbon number is the alkoxyl of 1～4. As the example of alkoxyl, specifically can enumerate: methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, cyclohexyloxy.
When in the aryl that the aforementioned carbon number being previously mentioned is 6～26 containing oxygen atom, aryloxy group can be formed. Preferably, selecting carbon number is the aryloxy group of 6～16, it is further preferred that selecting carbon number is the aryloxy group of 6～14, it is further preferred that selecting carbon atom is the aryloxy group of 6～10. As the example of aryloxy group, specifically can enumerate: phenoxy group, benzyloxy, 4-methylphenoxy, 3,5-dimethyl phenoxies, 4-methylbenzyloxy, 3-methylbenzyloxy, 2,6-diisopropyl benzyloxies, 1-naphthoxy.
When the alkyl that the carbon number being previously mentioned is 1～20, carbon number be 2～20 thiazolinyl, carbon number be 6～26 aryl, carbon number be 1～20 alkoxyl, carbon number be 6～26 aryloxy group replaced by halogen atom after, successively accordingly formed carbon number be 1～20 haloalkyl, carbon number be 2～20 haloalkenyl group, carbon number be 6～26 halogenated aryl, carbon number be 1～20 halogenated alkoxy, carbon number be the haloaryloxy of 6～26, wherein halogen atom is F, Cl, Br, it is preferred to F, Cl. In the halo group formed, part hydrogen atom or whole hydrogen atom are replaced by halogen atom, and the number of halogen atom can be 1,2,3 or 4.
Preferably, selecting carbon number is the haloalkyl of 1～10, carbon number is the haloalkenyl group of 2～10, carbon number is the halogenated aryl of 6～16, carbon number is the halogenated alkoxy of 1～10, carbon number is the haloaryloxy of 6～16, further preferably, the halo chain-like alkyl selecting carbon number to be 1～6, carbon number is the halogenated cycloalkyl of 3～8, carbon number is the haloalkenyl group of 2～6, carbon number is the halogenated aryl of 6～14, carbon number is the halogenated alkoxy of 1～6, carbon number is the haloaryloxy of 6～14, still more preferably, the halo chain-like alkyl selecting carbon number to be 1～4, carbon number is the halogenated cycloalkyl of 5～7, carbon number is the haloalkenyl group of 2～5, carbon atom is the halogenated aryl of 6～10, carbon number is the halogenated alkoxy of 1～4, carbon atom is the haloaryloxy of 6～10.
As the example of halo group, specifically can enumerate: trifluoromethyl (-CF3), 2-fluoro ethyl, 3-fluorine n-pro-pyl, 2-fluorine isopropyl, 4-fluorine normal-butyl, 3-fluorine sec-butyl, 5-fluorine n-pentyl, 4-fluorine isopentyl, 1-is fluoride-based, 3-fluorine pi-allyl, the fluoro-4-hexenyl of 6-, adjacent fluorophenyl, to fluorophenyl, between fluorophenyl, 4-trifluoromethylphenyl, 2,6-difluoromethyl phenyl, the fluoro-1-naphthyl of 2-, fluoro-methoxy, 1-fluorine ethyoxyl, the fluoro-positive propoxy of 2-, the fluoro-isopropoxy of 1-, the fluoro-n-butoxy of 3-, the fluoro-n-pentyloxy of 4-, 2,2-difluoromethyl propoxyl group, the fluoro-positive hexyloxy of 5-, 1,1,2-trifluoromethyl propoxyl group, the fluoro-n-heptyl oxygen base of 6-, the fluoro-n-octyl oxygen base of 7-, the fluoro-cyclopentyloxy of 3-, the fluoro-2-methylcyclopentoxy of 4-, the fluoro-cyclohexyloxy of 3-, 3-fluorine ring oxygen in heptan base, 4-fluoro-2-methyl ring oxygen in heptan base, 3-fluorine ring octyloxy, 4-fluorophenoxy, 3-fluorophenoxy, 2-fluorophenoxy, 3,5-difluoro phenoxy groups, 2,6-difluoro phenoxy groups, 2,3-difluoro phenoxy groups, 2,6-bis-fluoro-4-methylphenoxy, 3-(2-fluoro ethyl) phenoxy group, 2-(1-fluoro ethyl) phenoxy group, 3,5-difluoro benzyloxies, 2-fluorine benzyloxy, the fluoro-1-naphthoxy of 2-. in above-mentioned concrete example, F can be replaced by Cl and/or Br.
Carbon number is 1～20 alkyl, carbon number be 2～20 thiazolinyl, carbon number be 6～26 aryl replaced by sulfonic group or sulfonyl after, corresponding form sulfonic group alkyl, sulfonic group thiazolinyl, sulfonic group aryl, alkyl sulphonyl, alkenylsufonyl, aryl sulfonyl. Part hydrogen atom in abovementioned alkyl, thiazolinyl, aryl or whole hydrogen atom can be replaced by sulfonic group; sulfonic number can be 1 or 2; same; part hydrogen atom in abovementioned alkyl, thiazolinyl, aryl or whole hydrogen atom can be replaced by sulfonyl, and the number of sulfonyl can be 1 or 2.
As containing sulfonyl example, specifically can enumerate: methyl sulphonyl, ethylsulfonyl, n-pro-pyl sulfonyl, isopropelsulfonyl, normal-butyl sulfonyl, iso-butylsulfonyl, tert. butylsulfonyl, n-pentyl sulfonyl, isopentyl sulfonyl, neopentyl sulfonyl, 2, 3-dimethyl propyl sulfonyl, 1-ethyl propyl sulfonyl, n-hexyl sulfonyl, Cyclopentylsulfonyl, cyclohexylsulfonyl, suberyl sulfonyl, ring octyl group sulfonyl, n-heptyl sulfonyl, n-octyl sulfonyl, suberyl sulfonyl, ring octyl group sulfonyl, acrylic sulfonyl, cyclobutenyl sulfonyl, pentenyl sulfonyl, hexenyl sulfonyl, heptenyl sulfonyl, octenyl sulfonyl, phenyl sulfonyl, 4-Methyl benzenesulfonyl base.
In addition contain sulfonic example, specifically can enumerate: sulfonomethyl, 2-sulfonic group ethyl, 3-sulfonic group n-pro-pyl, 4-sulfonic group normal-butyl, the sulfonic group tert-butyl group, 2-sulfonic group n-pentyl, 3-sulfonic group isopentyl, 6-sulfonic group n-hexyl, 2-sulfonic group cyclopenta, 4-sulfonic group cyclohexyl, sulfonic group acrylic, sulfonic group cyclobutenyl, sulfonic group pentenyl, sulfonic group hexenyl, sulfonic group heptenyl, sulfonic group octenyl, sulfonic group phenyl, 4-sulfonic acid methyl phenyl.
It addition, in the compound shown in above-mentioned Formulas I～Formula VII, R11、R12、R13、R14、R15In at least one be halogen atom, halogen atom is preferably F or Cl, R21、R22、R23、R24In at least one be halogen atom, halogen atom is preferably F or Cl, R31、R32、R33、R34In at least one be halogen atom, halogen atom is preferably F or Cl, R41、R42、R43、R44In at least one be halogen atom, halogen atom is preferably F or Cl, R51、R52、R53、R54In at least one be halogen atom, halogen atom is preferably F or Cl, R61、R62、R63In at least one be halogen atom, it is preferred to F or Cl, R71、R72、R73In at least one be halogen atom, halogen atom is preferably F or Cl.
As the example of nitrogen heterocyclic ring-boron trifluoride coordination compound, shown in specific as follows:
In this application, the nitrogen heterocyclic ring being previously mentioned-boron trifluoride coordination compound can synthesize according to the synthetic method of existing routine, for instance is referred to patent: CN200780033378.X.
In above-mentioned electrolyte, described silica phosphoric ester compound is at least one in the compound shown in following formula VIII, Formula IX:
In above-mentioned Formula VIII, Formula IX, R81、R82、R83、R84、R85、R86、R87、R88、R89、R91、R92、R93、R94、R95、R96、R97、R98、R99Be each independently selected from hydrogen atom, halogen atom, carbon number be 1～10 alkyl, carbon number be 2～10 thiazolinyl, carbon number be 6～10 aryl, carbon number be 1～10 haloalkyl, carbon number be 1～10 alkoxyl, carbon number be 6～10 aryloxy group, carbon number be 1～10 haloalkyl, carbon number be 6～10 halogenated aryl, carbon number be 1～10 halogenated alkoxy and haloaryloxy that carbon number is 6～10 in one, wherein, halogen atom is F, Cl, Br, it is preferably F, Cl and R81、R82、R83、R84、R85、R86、R87、R88, and R89All identical, R91、R92、R93、R94、R95、R96、R97、R98, and R99All identical.
In above-mentioned Formula VIII, Formula IX, substituent group is as described below.
Carbon number is the alkyl of 1～10, and alkyl can be chain-like alkyl, it is possible to for cycloalkyl, the ring hydrogen being positioned at cycloalkyl can be replaced by alkyl, and in described alkyl, the preferred lower limit of carbon number is 2,3,4,5, it is preferred that higher limit is 3,4,5,6,8,9. Preferably, selecting carbon number is the chain-like alkyl of 1～6, and carbon number is the cycloalkyl of 3～8, it is further preferred that selecting carbon number is the chain-like alkyl of 1～4, carbon number is the cycloalkyl of 5～7. As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, cyclopenta, cyclohexyl.
Carbon number is the thiazolinyl of 2～10, can be cyclic alkenyl radical, it is possible to for chain thiazolinyl. It addition, the number of double bond is preferably 1 in thiazolinyl. In described thiazolinyl, the preferred lower limit of carbon number is 3,4,5, it is preferred that higher limit is 3,4,5,6,8,9. Preferably, selecting carbon number is the thiazolinyl of 2～6, it is further preferred that selecting carbon number is the thiazolinyl of 2～5. As the example of thiazolinyl, specifically can enumerate: vinyl, pi-allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.
Carbon number is the aryl of 6～10, for instance phenyl, benzene alkyl, condensed-nuclei aromatics base such as naphthalene, and xenyl and condensed-nuclei aromatics base also can be replaced by alkyl or thiazolinyl. In described aryl, the preferred lower limit of carbon number is 7,8, it is preferred that higher limit is 8,9. Preferably, selecting carbon number is the aryl of 6～9. As the example of aryl, specifically can enumerate: phenyl, benzyl, xenyl, p-methylphenyl, o-tolyl, a tolyl.
When in the alkyl that the aforementioned carbon number being previously mentioned is 1～10 containing oxygen atom, alkoxyl can be formed. Preferably, selecting carbon number is the alkoxyl of 1～6, it is further preferred that selecting carbon number is the alkoxyl of 1～4. As the example of alkoxyl, specifically can enumerate: methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, cyclohexyloxy.
When in the aryl that the aforementioned carbon number being previously mentioned is 6～10 containing oxygen atom, aryloxy group can be formed. Preferably, selecting carbon atom is the aryloxy group of 6～9. As the example of aryloxy group, specifically can enumerate: phenoxy group, benzyloxy, 4-methylphenoxy, 3,5-dimethyl phenoxies, 4-methylbenzyloxy, 3-methylbenzyloxy, 2,6-diisopropyl benzyloxies, 1-naphthoxy.
When the alkyl that the carbon number being previously mentioned is 1～10, carbon number be 2～10 thiazolinyl, carbon number be 6～10 aryl, carbon number be 1～10 alkoxyl, carbon number be 6～10 aryloxy group replaced by halogen atom after, successively accordingly formed carbon number be 1～10 haloalkyl, carbon number be 2～10 haloalkenyl group, carbon number be 6～10 halogenated aryl, carbon number be 1～10 halogenated alkoxy, carbon number be the haloaryloxy of 6～10, wherein halogen atom is F, Cl, Br, it is preferred to F, Cl. In the halo group formed, part hydrogen atom or whole hydrogen atom are replaced by halogen atom, and the number of halogen atom can be 1,2,3 or 4.
Preferably, the halo chain-like alkyl selecting carbon number to be 1～6, carbon number is the halogenated cycloalkyl of 3～8, carbon number is the haloalkenyl group of 2～6, carbon number is the halogenated aryl of 6～9, carbon number is the halogenated alkoxy of 1～6, carbon number is the haloaryloxy of 6～9, further preferably, the halo chain-like alkyl selecting carbon number to be 1～4, carbon number is the halogenated cycloalkyl of 5～7, carbon number is the haloalkenyl group of 2～5, carbon atom is the halogenated aryl of 6～8, carbon number is the halogenated alkoxy of 1～4, carbon atom is the haloaryloxy of 6～8.
As the example of halo group, specifically can enumerate: trifluoromethyl (-CF3), 2-fluoro ethyl, 3-fluorine n-pro-pyl, 2-fluorine isopropyl, 4-fluorine normal-butyl, 3-fluorine sec-butyl, 5-fluorine n-pentyl, 4-fluorine isopentyl, 1-is fluoride-based, 3-fluorine pi-allyl, the fluoro-4-hexenyl of 6-, adjacent fluorophenyl, to fluorophenyl, between fluorophenyl, 4-trifluoromethylphenyl, 2,6-difluoromethyl phenyl, the fluoro-1-naphthyl of 2-, fluoro-methoxy, 1-fluorine ethyoxyl, the fluoro-positive propoxy of 2-, the fluoro-isopropoxy of 1-, the fluoro-n-butoxy of 3-, the fluoro-n-pentyloxy of 4-, 2,2-difluoromethyl propoxyl group, the fluoro-positive hexyloxy of 5-, 1,1,2-trifluoromethyl propoxyl group, the fluoro-n-heptyl oxygen base of 6-, the fluoro-n-octyl oxygen base of 7-, the fluoro-cyclopentyloxy of 3-, the fluoro-2-methylcyclopentoxy of 4-, the fluoro-cyclohexyloxy of 3-, 3-fluorine ring oxygen in heptan base, 4-fluoro-2-methyl ring oxygen in heptan base, 3-fluorine ring octyloxy, 4-fluorophenoxy, 3-fluorophenoxy, 2-fluorophenoxy, 3,5-difluoro phenoxy groups, 2,6-difluoro phenoxy groups, 2,3-difluoro phenoxy groups, 2,6-bis-fluoro-4-methylphenoxy, 3-(2-fluoro ethyl) phenoxy group, 2-(1-fluoro ethyl) phenoxy group, 3,5-difluoro benzyloxies, 2-fluorine benzyloxy, the fluoro-1-naphthoxy of 2-. in above-mentioned concrete example, F can be replaced by Cl and/or Br.
As the example of silica phosphoric ester compound, specifically can enumerate:
In this application, the silica phosphoric ester compound being previously mentioned can synthesize according to the synthetic method of existing routine, for instance is referred to document: US5830600.
It has been investigated that, when electrolyte includes nitrogen heterocyclic ring-boron trifluoride coordination compound mentioned above and silica phosphoric ester compound simultaneously, under the common synergism of the two, it is respectively formed the SEI film that can stop electrolyte decomposition on the positive and negative plate surface of lithium ion battery, forms, particularly in negative plate surface, solid electrolyte interface (SEI) film that impedance is little and fine and close;Further, since electrolyte contains nitrogen heterocyclic ring-boron trifluoride coordination compound and silica phosphoric ester compound simultaneously, it is also possible to adsorb the material such as oxygen and lithium oxide at positive pole; Additionally it is possible to the acidic materials produced in neutralization electrolyte, such as PF5、HF、CO2Deng, effectively reduce the corrosion to SEI film of these acidic materials; Thus it is known that under the synergism of the two, substantially increase the cycle performance of lithium ion battery, for instance lithium ion battery is respectively provided with the cycle performance of excellence under 4.6V high voltage and at 25 DEG C and 45 DEG C; Meanwhile, the high temperature safety of electrolyte and memory property have also been obtained and significantly improve.
In above-mentioned electrolyte, the 0.05%～10% of the gross weight that content is electrolyte of described nitrogen heterocyclic ring-boron trifluoride coordination compound, the content of described nitrogen heterocyclic ring-boron trifluoride coordination compound is preferably the 0.1%～4% of the gross weight of electrolyte, the 0.1%～10% of the gross weight that content is electrolyte of described silica phosphoric ester compound, the 1%～4% of the gross weight that content is electrolyte of described silica phosphoric ester compound.
If in the electrolytic solution, nitrogen heterocyclic ring-boron trifluoride coordination compound content is excessive, then can cause being formed on positive and negative plate surface thicker SEI film, reduce the conductive performance of lithium ion, worsen lithium ion battery cycle performance at ambient and elevated temperatures; And the content of silica phosphoric ester compound is excessive, also very thick and stable SEI film can be formed on positive and negative plate surface, the impedance making positive and negative plate is greatly increased, and reduces the conductive performance of lithium ion, worsens lithium ion battery cycle performance at ambient and elevated temperatures.
If in the electrolytic solution, nitrogen heterocyclic ring-boron trifluoride coordination compound content is too small, it is impossible to be effectively improved lithium ion battery cycle performance at ambient and elevated temperatures, cycle performance especially under high pressure; And the content of silica phosphoric ester compound is too small, lithium ion battery cycle performance at ambient and elevated temperatures, cycle performance especially under high pressure can not be improved equally.
In above-mentioned electrolyte, described organic solvent can be non-aqueous organic solvent, and it is 1～8 and the compound containing at least one ester group that described organic solvent is preferably carbon number.
Example as organic solvent, can enumerate: ethylene carbonate, propene carbonate, butylene, fluorinated ethylene carbonate, Ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl n-butyrate..
In above-mentioned electrolyte, described lithium salts can be organic lithium salt, it is possible to for inorganic lithium salt, specifically, can contain at least one in fluorine element, boron element, P elements in described lithium salts. Preferably, described lithium salts is selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), tetrafluoro oxalic acid lithium phosphate (LiTFOP), LiN (SO2RF)2、LiN(SO2F)(SO2RF), double; two trifluoromethanesulfonimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), double; two (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (being abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4) at least one in (being abbreviated as LiDFOB), wherein, substituent RF=-CnF2n+1Saturated perfluoroalkyl, n is the integer of 1～10, it is preferred to the integer of 1～4, and the integer that 2n+1 is more than zero.It is particularly preferably LiPF6And/or LiN (SO2RF)2. Described lithium salts concentration in the electrolytic solution is 0.5M～2M (M=molL-1)。
In this application, the preparation method of electrolyte selects conventional method, for instance can by organic solvent, lithium salts and additive mix homogeneously.
The another object of the application there are provided lithium ion battery, and described lithium ion battery includes electrolyte, the positive plate containing positive electrode active materials, the negative plate containing negative active core-shell material and isolating membrane.
In above-mentioned lithium ion battery, described positive plate also includes binding agent and conductive agent, is coated on plus plate current-collecting body by the anode sizing agent including positive electrode active materials, binding agent and conductive agent, treats that anode sizing agent obtains positive plate after drying. Same, the cathode size including negative active core-shell material, binding agent and conductive agent is coated on negative current collector, treats that cathode size obtains negative plate after drying.
Preferably, described positive electrode active materials is selected from cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material, LiFePO 4, LiFePO4 (LiFePO4), LiMn2O4 (LiMnO2) at least one, for instance the mixture of cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material can as positive electrode active materials. As the example of cobalt nickel lithium manganate ternary material, specifically can enumerate: LiNi1/3Co1/3Mn1/3O2, nickle cobalt lithium manganate LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2。
Preferably, described negative active core-shell material is graphite and/or silicon.
In above-mentioned lithium ion battery, the concrete kind of lithium battery diaphragm is not exposed to concrete restriction, can be any diaphragm material used in existing lithium ion battery, for instance polyethylene, polypropylene, Kynoar and their multilayer complex films, but be not limited only to these.
Embodiment
The application is further described below by way of instantiation. But these examples are only exemplary, the protection domain of the application do not constituted any restriction.
In following embodiment, comparative example and test example, reagent, material and the instrument used be not as having special explanation, being conventional reagent, conventional material and conventional instrument, all commercially available, wherein involved reagent obtains also by conventional synthesis process synthesis.
In following embodiment, comparative example and test example, used reagent is as follows:
Additive:
Nitrogen heterocyclic ring-boron trifluoride coordination compound: the compound 1～compound 7 being previously mentioned.
Silica phosphoric ester compound: the silica phosphide 1 being previously mentioned.
Lithium salts: lithium hexafluoro phosphate (LiPF6)。
Organic solvent: ethylene carbonate (EC), Ethyl methyl carbonate (EMC).
Positive electrode active materials: lithium-nickel-manganese-cobalt ternary material (LiNi1/3Co1/3Mn1/3O2)。
Isolating membrane: using PE porous polymer film as isolating membrane.
The preparation of embodiment 1～36 lithium ion battery (following be all called for short battery) 1～36
Battery 1～36 is all prepared by the following method:
(1) prepared by negative plate
It is graphite by negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber, thickening agent sodium carboxymethyl cellulose according to weight ratio: acetylene black: butadiene-styrene rubber: sodium carboxymethyl cellulose=95: mix at 2: 2: 1, after adding deionized water, it is sufficiently stirred for mixing, forms uniform cathode size; This slurry is coated on negative current collector Copper Foil, then dries, cold pressing, obtain negative plate.
(2) prepared by positive plate
By positive electrode active materials lithium-nickel-manganese-cobalt ternary material, conductive agent acetylene black, binding agent polyvinylidene fluoride by weight for lithium-nickel-manganese-cobalt ternary material: acetylene black: polyvinylidene fluoride=96: mix at 2: 2, add solvent N-methyl pyrilidone, after being sufficiently stirred for mixing, form uniform anode sizing agent;This slurry is coated on plus plate current-collecting body aluminium foil, then dries, cold pressing, obtain positive plate.
(3) prepared by electrolyte
Electrolyte 1～36 is all prepared by the following method:
In the argon gas atmosphere glove box of water content < 10ppm, by EC, EMC according to weight ratio be EC: EMC=3: 7 mix after, obtain mixed solvent, then lithium salts LiPF that will be fully dry6It is dissolved in above-mentioned mixed solvent, is then added thereto to nitrogen heterocyclic ring-boron trifluoride coordination compound and silica phosphoric ester compound, after stirring, it is thus achieved that electrolyte, wherein LiPF6Concentration be 1mol/L.
(4) preparation of battery
Battery 1～36 all prepares by the following method:
Positive plate, isolating membrane, negative plate being folded in order, make isolating membrane be between positive/negative plate to play the effect of isolation, then winding obtains naked battery core; Naked battery core is placed in outer package paper tinsel, the above-mentioned electrolyte prepared is injected in dried battery, is then passed through the operations such as Vacuum Package, standing, chemical conversion, shaping, it is thus achieved that battery.
In the above-mentioned process preparing battery, the kind of nitrogen heterocyclic ring-boron trifluoride coordination compound used in electrolyte selected in each battery, each electrolyte and the content of content and silica phosphoric ester compound thereof, as shown in table 1 below.
In table 1 below, the content of nitrogen heterocyclic ring-boron trifluoride coordination compound and the content of silica phosphoric ester compound are the percetage by weight that the total weight based on electrolyte obtains.
Table 1
Comparative example 1～21 lithium ion battery (following be all called for short battery) 1#～21#Preparation
Comparative example 1～21
Battery 1#～21#All it is prepared by the following method:
Repeating the preparation of battery 1 in embodiment 1, wherein in the preparation of electrolyte, change the nitrogen heterocyclic ring-kind of boron trifluoride coordination compound, content and/or the content of change silica phosphoric ester compound, all the other conditions are all constant.
In the above-mentioned process preparing battery, the kind of nitrogen heterocyclic ring-boron trifluoride coordination compound used in electrolyte selected in each battery, each electrolyte and the content of content and silica phosphoric ester compound thereof, as shown in table 2 below.
In table 2 below, the content of nitrogen heterocyclic ring-boron trifluoride coordination compound and the content of silica phosphoric ester compound are the percetage by weight that the total weight based on electrolyte obtains.
Table 2
Note: in table 2, "-" represents and is not added with any kind of material.
Test case
(1) test of electrochemical impedance spectroscopy (ElectrochemicalImpedanceSpectroscopy is abbreviated as EIS)
The battery prepared in embodiment and comparative example all carries out following test:
At 25 DEG C, by the constant current with 0.5C to battery discharge to 3.0V, again with 0.5C constant current discharge to 3.85V, then with the constant voltage of 3.85V, battery is charged to electric current less than 0.05C, now the capacity of battery reaches completely to fill the 50% of capacity, then uses VMP3 electrochemical workstation, under 25 DEG C of constant temperatures, battery is carried out EIS test, obtaining Charge-transfer resistance Rct, test result is as shown in Table 3 below.
(2) the normal-temperature circulating performance test of battery
The battery prepared in embodiment and comparative example all carries out following test:
At 25 DEG C, first with the constant current of 1C, battery is charged to 4.6V, further with 4.6V constant-potential charge to electric current for 0.025C, then with the constant current of 1C by battery discharge to 3.0V, this is a charge and discharge cycles process, and this discharge capacity is the discharge capacity of the 1st circulation.Battery carries out repeatedly cycle charge discharge electrical testing in a manner described, and detection obtains the discharge capacity of the 100th circulation, and is calculated the circulation volume conservation rate of battery by following formula. It addition, test result is as shown in Table 3 below.
Capability retention (%) after 100 circulations of battery=[discharge capacity of the discharge capacity/1st time circulation of the 100th circulation] × 100%
(3) the high temperature cyclic performance test of battery
The battery prepared in embodiment and comparative example all carries out following test:
At 45 DEG C, first with the constant current of 1C, battery is charged to 4.6V, further with 4.6V constant-potential charge to electric current for 0.025C, then with the constant current of 1C by battery discharge to 3.0V, this is a charge and discharge cycles process, and this discharge capacity is the discharge capacity of the 1st circulation. Battery carries out repeatedly cycle charge discharge electrical testing in a manner described, and detection obtains the discharge capacity of the 100th circulation, and is calculated the capability retention after the circulation of battery by following formula. It addition, test result is as shown in Table 3 below.
Capability retention (%) after 100 circulations of battery=[discharge capacity of the discharge capacity/1st time circulation of the 100th circulation] × 100%
Table 3
Related data from above-mentioned table 3, carries out analyzing as follows:
(1) test result analysis of EIS
By to battery 2#, battery 3#And battery 4 and battery 1#Test obtain as a result, it is possible to learn, only add silica phosphoric ester compound, Rct value is smaller; Only adding nitrogen heterocyclic ring-boron trifluoride coordination compound, Rct value is relatively larger; When containing silica phosphoric ester compound and nitrogen heterocyclic ring-boron trifluoride coordination compound in electrolyte simultaneously, more only adding the situation of nitrogen heterocyclic ring-boron trifluoride coordination compound, Rct value is less.
Being contrasted by the test result of the battery obtained, it is possible to learn, when the addition of silica phosphoric ester compound is too much, Rct value is also bigger; Same, if the content of nitrogen heterocyclic ring-boron trifluoride coordination compound is too much, Rct value is also bigger.
(2) test result analysis of cycle performance
Capability retention after the circulation obtained by battery 1～36 and battery 1#Capability retention after the circulation obtained is it can be seen that containing nitrogen heterocyclic ring-boron trifluoride coordination compound and silica phosphoric ester compound in electrolyte, battery has higher capability retention, and battery has the cycle performance of excellence under high temperature and room temperature.
By battery 1#～9#Capability retention after the circulation obtained, it is possible to learn, electrolyte 1#In do not add any additive so that organic solvent can produce more side reaction in pole piece, causes that the capability retention of battery is low.
At battery 2#With battery 3#In, nitrogen heterocyclic ring-boron trifluoride coordination compound, silica phosphoric ester compound is added respectively in respective electrolyte, SEI film owing to being formed can't stop the side reaction between active substance and electrolyte effectively so that the cycle performance of battery substantially can not get improve.
Due at battery 4#, battery 5#With battery 7#In, the weight percentage of nitrogen heterocyclic ring-boron trifluoride coordination compound and/or silica phosphoric ester compound is very little, the SEI film formed can not have the feature of compactness and stability concurrently, cannot effectively stop the side reaction between active substance and electrolyte, make battery cycle performance under high temperature and room temperature can not get effective improvement.
At battery 6#, battery 8#, battery 9#In, nitrogen heterocyclic ring-boron trifluoride coordination compound and/or silica phosphoric ester compound content are too much, too much nitrogen heterocyclic ring-boron trifluoride coordination compound and silica phosphoric ester compound remain in the electrolytic solution, continue to react in pole piece, cause interface impedance to become big, worsen battery cycle performance under high temperature and room temperature.
In battery 1～8, the content of silica phosphoric ester compound is 2%, add nitrogen heterocyclic ring-boron trifluoride coordination compound that content is 0.05%～10%, SEI film densification, stable can be formed, stop the side reaction between active substance and electrolyte, make battery have higher capability retention after circulating under high temperature and room temperature.
In battery 4 and battery 9～14, the content of nitrogen heterocyclic ring-boron trifluoride coordination compound is 2%, add the silica phosphoric ester compound that content is 0.1%～10%, SEI film densification, stable can be formed, stop the side reaction between active substance and electrolyte, make battery have higher capability retention after circulating under high temperature and room temperature. Same, the capability retention after battery 15～36 is circulated is analyzed, and has analysis result same as described above.
Can be seen that in from the above, when nitrogen heterocyclic ring-boron trifluoride coordination compound and silica phosphoric ester compound simultaneously in electrolyte, improving the capability retention after battery circulates under high temperature and room temperature, battery has the cycle performance of excellence under high temperature and room temperature.
In sum: in the electrolytic solution, when the content of nitrogen heterocyclic ring-boron trifluoride coordination compound is too small or excessive and it is too small or excessive to work as silica phosphoric ester compound content, all can not form fine and close, stable, the good SEI film of interface performance, it is impossible to obtain the battery of good cycle under high temperature and room temperature simultaneously. Nitrogen heterocyclic ring-boron trifluoride the coordination compound of 0.05%～10% and the silica phosphoric ester compound of 0.1%～10% is contained when electrolyte, especially containing the nitrogen heterocyclic ring-boron trifluoride coordination compound of 0.1%～4.0% and the silica phosphoric ester compound of 1%～4%, battery cycle performance under high temperature and room temperature is all comparatively excellent.
The announcement of book according to the above description, above-mentioned embodiment can also be carried out suitable change and amendment by the application those skilled in the art. Therefore, the application is not limited to detailed description of the invention disclosed and described above, should also be as some modifications and changes of the application falling in the protection domain of claims hereof.

Claims (10)

1. an electrolyte, it is characterized in that, including organic solvent, lithium salts and additive, described additive includes nitrogen heterocyclic ring-boron trifluoride coordination compound and silica phosphoric ester compound, wherein, described nitrogen heterocyclic ring is at least one in the heterocycle containing pyridine radicals, the heterocycle containing pyridazinyl, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, heterocycle containing pyrrole radicals, the heterocycle of pyrazolyl containing and the heterocycle containing imidazole radicals.
2. electrolyte according to claim 1, it is characterised in that described nitrogen heterocyclic ring-boron trifluoride coordination compound is at least one in the compound shown in following formula I, Formula II, formula III, Formulas I V, Formula V, Formula IV and Formula VII:
Wherein, R11、R12、R13、R14、R15、R21、R22、R23、R24、R31、R32、R33、R34、R41、R42、R43、R44、R51、R52、R53、R54、R61、R62、R63、R71、R72、R73It is each independently selected from hydrogen atom, halogen atom, carbon number is the alkyl of 1～20, carbon number is the thiazolinyl of 2～20, carbon number is the aryl of 6～26, carbon number is the alkoxyl of 1～20, carbon number is the aryloxy group of 6～26, and above-mentioned carbon number is the alkyl of 1～20, carbon number is the thiazolinyl of 2～20, carbon number is the aryl of 6～26, carbon number is the alkoxyl of 1～20, carbon number is that the aryloxy group of 6～26 is by halogen atom, sulfonic group or sulfonyl replace the one in the group formed, wherein, halogen atom is F, Cl, Br, preferred F, Cl, and
R11、R12、R13、R14、R15In at least one be halogen atom, R21、R22、R23、R24In at least one be halogen atom, R31、R32、R33、R34In at least one be halogen atom, R41、R42、R43、R44In at least one be halogen atom, R51、R52、R53、R54In at least one be halogen atom, R61、R62、R63In at least one be halogen atom, R71、R72、R73In at least one be halogen atom, wherein, described halogen atom is F, Cl.
3. electrolyte according to claim 2, it is characterised in that R11、R12、R13、R14、R15、R21、R22、R23、R24、R31、R32、R33、R34、R41、R42、R43、R44、R51、R52、R53、R54、R61、R62、R63、R71、R72、R73It is each independently selected from F, carbon number is the chain-like alkyl of 1～4, carbon number is the cycloalkyl of 5～7, carbon number is the thiazolinyl of 2～5, carbon number is the aryl of 6～9, carbon number is the alkoxyl of 1～4, carbon atom is the aryloxy group of 6～10, carbon number is the halo chain-like alkyl of 1～4, carbon number is the halogenated cycloalkyl of 5～7, carbon number is the haloalkenyl group of 2～5, carbon atom is the halogenated aryl of 6～10, carbon number is the halogenated alkoxy of 1～4, and the one in the haloaryloxy that carbon atom is 6～10.
4. electrolyte according to claim 1, it is characterised in that described nitrogen heterocyclic ring-boron trifluoride coordination compound is at least one in following coordination compound:
5. electrolyte according to claim 1, it is characterised in that described silica phosphoric ester compound is at least one in the compound shown in following formula VIII, Formula IX:
Wherein, R81、R82、R83、R84、R85、R86、R87、R88、R89、R91、R92、R93、R94、R95、R96、R97、R98、R99Be each independently selected from hydrogen atom, halogen atom, carbon number be 1～10 alkyl, carbon number be 2～10 thiazolinyl, carbon number be 6～10 aryl, carbon number be 1～10 haloalkyl, carbon number be 1～10 alkoxyl, carbon number be 6～10 aryloxy group, carbon number be 1～10 haloalkyl, carbon number be 6～10 halogenated aryl, carbon number be 1～10 halogenated alkoxy and haloaryloxy that carbon number is 6～10 in one, wherein, halogen atom is F, Cl, Br, and R81、R82、R83、R84、R85、R86、R87、R88, and R89All identical, R91、R92、R93、R94、R95、R96、R97、R98, and R99All identical.
6. electrolyte according to claim 1, it is characterised in that described silica phosphoric ester compound is at least one in following compound:
7. electrolyte according to claim 1, it is characterised in that the 0.05%～10% of the gross weight that content is electrolyte of described nitrogen heterocyclic ring-boron trifluoride coordination compound, and/or,
The 0.1%～10% of the gross weight that content is electrolyte of described silica phosphoric ester compound.
8. electrolyte according to claim 1, it is characterized in that, described organic solvent is at least one in ethylene carbonate, Allyl carbonate, butylene, fluorinated ethylene carbonate, Ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate and ethyl n-butyrate..
9. electrolyte according to claim 1, it is characterised in that
Described lithium salts is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate, LiN (SO2RF)2、LiN(SO2F)(SO2RF), double; two trifluoromethanesulfonimide lithium, double; two (fluorine sulphonyl) imine lithium, di-oxalate lithium borate, at least one in difluorine oxalic acid boracic acid lithium, wherein, RF=-CnF2n+1, n is the integer of 1～10, it is particularly preferred to for LiPF6And/or LiN (SO2RF)2; And/or
Described lithium salts concentration in the electrolytic solution is 0.5molL-1～2molL-1。
10. a lithium ion battery, it is characterised in that include the positive plate containing positive electrode active materials, containing the electrolyte according to any one of the negative plate of negative active core-shell material, isolating membrane and claim 1～9.
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CN111129587A (en) * 2019-12-20 2020-05-08 杉杉新材料（衢州）有限公司 Non-aqueous electrolyte for lithium ion battery and lithium ion battery thereof
WO2022127194A1 (en) * 2020-12-17 2022-06-23 北京卫蓝新能源科技有限公司 Sulfur-based boron trifluoride salt electrolyte containing unsaturated heterocycle, preparation method therefor and use thereof

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