CN105826608A - Electrolyte and lithium ion battery containing electrolyte - Google Patents
Electrolyte and lithium ion battery containing electrolyte Download PDFInfo
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- CN105826608A CN105826608A CN201610352295.8A CN201610352295A CN105826608A CN 105826608 A CN105826608 A CN 105826608A CN 201610352295 A CN201610352295 A CN 201610352295A CN 105826608 A CN105826608 A CN 105826608A
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to an electrolyte and a lithium ion battery containing the electrolyte .The electrolyte comprises lithium salt, organic solvent and additives, wherein the additives include a dimerization ester compound and a dinitrile compound containing an ether bond, and the dimerization ester compound includes carbonic acid ester dimer, carboxylic acid ester dimer and sulfonated lactone dimer .The electrolyte can improve the cycle performance, rate capability and high-temperature memory performance of the lithium ion battery on high voltage.
Description
Technical field
The application relates to technical field of lithium ion, specifically, relates to a kind of electrolyte and includes the lithium ion battery of this electrolyte.
Background technology
In recent years, fast development along with electronic product, the flying power of lithium ion battery is had higher requirement, wherein the principal element of decision lithium ion battery flying power is battery capacity, correspondingly, people it is also proposed higher requirement to the energy density of lithium ion battery, and in order to improve the energy density of lithium ion battery, exploitation high-voltage lithium ion batteries is one of effective method.However as the raising of voltage, the moisture in electrolyte and the reaction of other composition in electrolyte can be accelerated, also can produce Fluohydric acid. (HF), the performance such as circulation of lithium ion battery can be reduced, had a strong impact on performance of lithium ion battery.The performance promoting lithium ion battery by optimizing electrolyte is counted as one of maximally effective approach.
Although linear carbonate dimer, chain carboxylate dimer, chain sulphonic acid ester dimer or phosphate ester can improve high-temperature storage performance, initial charge/discharge performance, safety, cycle characteristics etc..Excessive yet with its viscosity, cause and pole piece and barrier film are infiltrated difficulty, particularly under high compacted density, battery core performance is caused adverse influence.
In consideration of it, special, the application is proposed.
Summary of the invention
The primary goal of the invention of the application is to propose a kind of electrolyte.
Second goal of the invention of the application is to propose a kind of lithium ion battery containing this electrolyte.
In order to complete present invention purpose, the technical scheme of employing is:
The application relates to a kind of electrolyte, including lithium salts, organic solvent and additive, containing additive A and additive B in described additive, at least one in dimer ester compounds of described additive A, described dimer ester compounds includes carbonic ester dimer, carboxylate dimer and sultone dimer；At least one in the dinitrile compound with ehter bond of described additive B.
Preferably, the structural formula of described carbonic ester dimer is as shown in formula I:
In formula I, R11、R13The most independent is respectively selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted C2～12Alkynyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C5～22Heterocyclic base；Substituent group is selected from halogen, C6～26Aryl, C3～8Cycloalkyl；
R12Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C6～26Arlydene, by least one ehter bond and at least one substituted or unsubstituted C1～12The group of alkylidene composition, substituent group is selected from halogen；
Preferably, described carboxylate dimer structure formula is as shown in formula II:
In formula II, R21、R23The most independent is respectively selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted C2～12Alkynyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C5～22Heterocyclic base；Substituent group is selected from halogen, C6～26Aryl, C3～8Cycloalkyl；
R22Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C6～26Arlydene, by least one ehter bond and at least one substituted or unsubstituted C1～12The group of alkylidene composition, substituent group is selected from halogen.
Preferably, described sultone dimer structure formula is as shown in formula III:
In formula III, R31、R33The most independent is respectively selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted C2～12Alkynyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C5～22Heterocyclic base；Substituent group is selected from halogen, C6～26Aryl, C3～8Cycloalkyl；
R32Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C6～26Arlydene, by least one ehter bond and at least one substituted or unsubstituted C1～12The group of alkylidene composition, substituent group is selected from halogen.
Preferably, there is the structural formula of dinitrile compound of ehter bond described in as shown in formula IV:
R41、R42、R43The most independent is respectively selected from C1～5Alkylidene, C2～5Alkenylene, m is the integer of 1～5.
Preferably, described have the dinitrile compound of ehter bond selected from 3,5-dioxa-pimelic dinitrile, 1,4-bis-(2-cyanoethoxy) butane, ethylene glycol bisthioglycolate (2-cyano ethyl) ether, diethylene glycol two (2-cyano ethyl) ether, triethylene glycol two (2-cyano ethyl) ether, TEG two (2-cyano ethyl) ether, 1,3-bis-(2-cyanoethoxy) propane, 1,4-bis-(2-cyanoethoxy) butane, 1, at least one in 5-bis-(2-cyanoethoxy) pentane, ethylene glycol bisthioglycolate (4-cyanobutyl) ether:
Preferably, the total content of described additive A and additive B be electrolyte gross weight 0.01%～10%.
Preferably, described additive also includes addition of C, at least one in ether compound, nitrile compound, cyclic ester compounds containing sulfur-to-oxygen double bond, cyclic carbonate compound, compound containing carbon-to-nitrogen double bond of described addition of C；
At least one in substituted or unsubstituted alkyl ether of described ether compound, substituent group is halogen；
Described nitrile compound is selected from the alkane containing 1～5 cyano group, the alkene containing 1～5 cyano group at least one；
At least one in cyclic sulfates, cyclic sulfite, sultone of the described cyclic ester compounds containing sulfur-to-oxygen double bond；
The described compound containing carbon-to-nitrogen double bond is for selected from containingAt least one in the compound of-N=C=N-.
Preferably, described ether compound is selected from substituted or unsubstituted C1～12At least one in alkyl ether, substituent group is halogen；
Described nitrile compound is selected from the C containing 1～4 cyano group2～12Alkane, C containing 1～4 cyano group2～12In alkene at least one；
At least one in the compound shown in formula V 1, formula V 2, formula V 3 of the described cyclic ester compounds containing sulfur-to-oxygen double bond: as described at least one in compound as shown in formula V 4 of cyclic carbonate compound:
R51、R52、R53、R54The most independent is respectively selected from substituted or unsubstituted C1～4Alkylidene, substituted or unsubstituted C2～4Alkenylene；Substituent group is selected from halogen, C2～4Thiazolinyl.
Preferably, addition of C is selected from 1-ethyoxyl-propane, 2-trifluoromethyl-3-methoxyl group perflenapent, 1, 1, 2, 2-tetra-fluoro ethyl-2', 2', 3', 3'-tetrafluoro propyl ether, acetonitrile, propionitrile, butyronitrile, valeronitrile, butene nitrile, 3-methyl butene nitrile, Cyanoacetyl-Cyacetazid, succinonitrile, glutaronitrile, adiponitrile, rich horse dintrile, sulfuric acid vinyl ester, sulphuric acid propylene, propylene sulfite, 1, 3-N-morpholinopropanesulfonic acid lactone, 1, 4-butyl sultone, acrylic-1, 3-sultones, vinylene carbonate, fluorinated ethylene carbonate, fluoro vinylene carbonate, 1, 2-bis-fluoro vinylene carbonate, vinylethylene carbonate, at least one in dicyclohexylcarbodiimide；
It is furthermore preferred that the 0.01%～10% of the gross weight that the content of described addition of C is electrolyte.
The application further relates to a kind of lithium ion battery, including the positive plate containing positive electrode active materials, the electrolyte of negative plate, lithium battery diaphragm and the application containing negative active core-shell material.
The technical scheme of the application at least can have the advantages that
The electrolyte that the application provides includes ester dimer and has the dintrile of ehter bond, lithium ion battery cycle performance, high rate performance and high-temperature storage performance under high voltages can be improved, such as, improve lithium ion battery cycle performance and high rate performance and the storage performance at the high voltage of 4.4V～5V and 85 DEG C under the high voltage of 4.4V～5V.Additionally, also improve the security performance of lithium ion battery, such as, improve the thermal stability of lithium ion battery, at a temperature of 150 DEG C, the Heat stability is good of lithium ion battery, substantially without occurring smoldering, the on fire and phenomenon of blast.
Below in conjunction with specific embodiment, the application is expanded on further.Should be understood that these embodiments are merely to illustrate the application rather than limit scope of the present application.
Detailed description of the invention
The purpose of the application is to provide a kind of electrolyte, including lithium salts, organic solvent and additive, containing additive A and additive B in additive, at least one in dimer ester compounds of additive A, dimer ester compounds includes carbonic ester dimer, carboxylate dimer and sultone dimer；At least one in the dinitrile compound with ehter bond of additive B.
As a kind of improvement of the application electrolyte, carbonic ester dimer structure formula is as shown in formula I:
In formula I, R11、R13The most independent is respectively selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted C2～12Alkynyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C5～22Heterocyclic base；Substituent group is selected from halogen, C6～26Aryl, C3～8Cycloalkyl；
R12Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C6～26Arlydene, by least one ehter bond and at least one substituted or unsubstituted C1～12The group of alkylidene composition, substituent group is selected from halogen.
As a kind of improvement of the application electrolyte, R11、R13The most independent is respectively selected from C1～6Alkyl, R12Selected from C1～6Alkylidene.
As a kind of improvement of the application electrolyte, the certain embodiments of carbonic ester dimer is as follows:
As a kind of improvement of the application electrolyte, carboxylate dimer structure formula is as shown in formula II:
In formula II, R21、R23The most independent is respectively selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted C2～12Alkynyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C5～22Heterocyclic base；Substituent group is selected from halogen, C6～26Aryl, C3～8Cycloalkyl；
R22Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C6～26Arlydene, by least one ehter bond and at least one substituted or unsubstituted C1～12The group of alkylidene composition, substituent group is selected from halogen.
As a kind of improvement of the application electrolyte, R21、R23The most independent is respectively selected from C1～6Alkyl, R22Selected from C1～12Alkylidene, ehter bond and two C1～6Alkylidene connects the divalent group obtained.
As a kind of improvement of the application electrolyte, the certain embodiments of carboxylate dimer is as follows:
As a kind of improvement of the application electrolyte, sultone dimer structure formula is as shown in formula III:
In formula III, R31、R33The most independent is respectively selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted C2～12Alkynyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C5～22Heterocyclic base；Substituent group is selected from halogen, C6～26Aryl, C3～8Cycloalkyl；
R32Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C6～26Arlydene, by least one ehter bond and at least one substituted or unsubstituted C1～12The group of alkylidene composition, substituent group is selected from halogen.
As a kind of improvement of the application electrolyte, R31、R33The most independent is respectively selected from C1～6Alkyl, R32Selected from C1～6Alkylidene.
As a kind of improvement of the application electrolyte, the certain embodiments of sultone dimer is as follows:
As a kind of improvement of the application electrolyte, there is the structural formula of dinitrile compound of ehter bond as shown in formula IV:
Wherein, R41、R42、R43The most independent is respectively selected from C1～5Alkylidene, C2～5Alkenylene, m is the integer of 1～5.
As a kind of improvement of the application electrolyte, R41、R42、R43The most independent is respectively selected from C1～5Alkylidene, m is 1 or 2.
In the structure above of the application:
Carbon number is the alkyl of 1～12, 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 the alkyl of preferred straight or branched.In described alkyl, the preferred lower limit of carbon number is 2,3,4,5, and preferred higher limit is 3,4,5,6,8,10,11.Preferably, the alkyl selecting carbon number to be 1～10, further preferably, the chain-like alkyl selecting carbon number to be 1～6, carbon number is the cycloalkyl of 3～8, still more preferably, the chain-like alkyl selecting carbon number to be 1～4, carbon number is the cycloalkyl of 5～7.Example as alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, hexyl, 2-Methyl pentyl, 3-Methyl pentyl, 1,1,2-trimethyl-propyl, 3,3 ,-dimethyl-butyl, heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, different heptyl, octyl group, nonyl, decyl.
Carbon number be the thiazolinyl of 2～12 can be cyclic alkenyl radical, it is possible to for chain thiazolinyl.And the thiazolinyl of preferred straight or branched.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, preferred higher limit 6,8,10,11.Preferably, the thiazolinyl selecting carbon number to be 2～10, it is further preferred that the thiazolinyl selecting carbon number to be 2～6, it is further preferred that the thiazolinyl selecting carbon number to be 2～5.As the example of thiazolinyl, specifically can enumerate: vinyl, pi-allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.Specifically chosen identical with thiazolinyl to alkynyl.
Carbon number be the alkylidene of 1～12 be straight or branched alkylidene, the preferred lower limit of the carbon number of alkylidene can be 1,2,3,4, preferred higher limit can be 6,7,8,9,10,11.As the example of alkylidene, specifically can enumerate: methylene, ethylene, 1,3-propylidene, 2-methyl isophthalic acid, 3-propylidene, 1,3-dimethylpropylidene, 1-methyl isophthalic acid, 2-ethylidene, 1,1-dimethylethylene, 1,2-dimethylethylene, tetramethylene, 1,5-pentylidene, 1,6-hexylidene, 1, Isosorbide-5-Nitrae, 4-tetramethyl butylidene, cyclopropylidene, 1,2-cyclopropylidene, 1,3-Asia cyclobutyl, sub-cyclobutyl, cyclohexylidene, Isosorbide-5-Nitrae-cyclohexylidene, 1,4-cycloheptylidene, cycloheptylidene, 1,5-cyclooctylene, cyclooctylene.
Carbon number be the alkenylene of 2～12 be straight or branched alkenylene, the number of the double bond in thiazolinyl and the position of double bond are not particularly limited, can according to practical situation select desired structure thiazolinyl.Particularly, the number of double bond can be 1,2,3 or 4.In described alkenylene, the preferred lower limit of the carbon number of alkenylene can be 2,3,4,5, and preferred higher limit can be 6,8,10,11.Example as alkenylene, specifically can enumerate: 1,2-ethenylidene, ethenylidene, propenylene, 2-allylidene, methyl isophthalic acid, 2-ethenylidene, ethyl-1,2-ethenylidene, 1,4-butenylidene, 1, the sub-amyl-2-thiazolinyl of 5-, 1,6-Asia hex-3-thiazolinyl, 1,7-Asia hept-3-thiazolinyl, 1,8-Asia oct-2-ene base.
Carbon number is the aryl of 6～26, such as phenyl, benzene alkyl, at least contains 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, the aryl selecting carbon number to be 6～16, it is further preferred that the aryl selecting carbon number to be 6～14, it is further preferred that the aryl selecting carbon number to be 6～9.As the example of aryl, specifically can enumerate: phenyl, benzyl, xenyl, p-methylphenyl, o-tolyl, a tolyl.
Carbon number is the heterocyclic base of 5～22, is selected from: furyl, thienyl, pyrrole radicals, thiazolyl, imidazole radicals, pyridine radicals, pyrazinyl, pyrimidine radicals, pyridazinyl, indyl, quinolyl etc..
Halogen is selected from fluorine, chlorine, bromine；And preferably fluorine, chlorine.
A kind of improvement as the application electrolyte, the dinitrile compound with ehter bond is at least one in following substances: 3, 5-dioxa-pimelic dinitrile (referred to as AM1), 1, 4-bis-(2-cyanoethoxy) butane (referred to as AM2), ethylene glycol bisthioglycolate (2-cyano ethyl) ether (referred to as AM3), diethylene glycol two (2-cyano ethyl) ether, triethylene glycol two (2-cyano ethyl) ether, TEG two (2-cyano ethyl) ether, 1, 3-bis-(2-cyanoethoxy) propane (AM4), 1, 4-bis-(2-cyanoethoxy) butane, 1, 5-bis-(2-cyanoethoxy) pentane and ethylene glycol bisthioglycolate (4-cyanobutyl) ether.
Preferably, the dinitrile compound with ehter bond is ethylene glycol bisthioglycolate (2-cyano ethyl) ether.
Wherein, the structural formula of the certain embodiments with the dinitrile compound of ehter bond is as follows:
3,5-dioxa-pimelic dinitrile (referred to as AM1)；
1,4-bis-(2-cyanoethoxy) butane (referred to as AM2)；
Ethylene glycol bisthioglycolate (2-cyano ethyl) ether (referred to as AM3)；
1,3-bis-(2-cyanoethoxy) propane (referred to as AM4).
In this application, ester dimer can obtain according to conventional synthetic method, see, for example, CN101359750B, and certain described ester dimer can also be by commercially available；The dinitrile compound with ehter bond can be obtained by existing synthetic method, can be found in CN201280006888.9, it is also possible to by commercially available, and its source is not exposed to concrete restriction.
As the gross weight that total content is electrolyte of a kind of improvement of the application electrolyte, ester dimer and the dintrile with ehter bond 0.01%～10%.It has been investigated that, when both total contents are less than 0.01%, electrolyte is not effectively form stable passivating film, and the high-temperature storage performance of lithium ion battery and high rate performance can not get improving substantially；When total content is more than 10%, the film formed is thicker, and impedance increases, and can reduce the cycle performance of lithium ion battery.It is further preferred that described ester dimer and 1～5% of the gross weight that dintrile total content is electrolyte with ehter bond.Furthermore, it is necessary to explanation, ester dimer is unrestricted with the content ratio of the dintrile with ehter bond.
In order to improve further the high-temperature storage performance of lithium ion battery and high rate performance and security performance, it is preferable that the weight ratio of described ester dimer and the dintrile with ehter bond is ester dimer: have dintrile=1:3～3:1 of ehter bond.
In above-mentioned electrolyte, it is preferable that described additive also includes addition of C, at least one in ether compound, nitrile compound, cyclic ester compounds containing sulfur-to-oxygen double bond, cyclic carbonate compound, compound containing carbon-to-nitrogen double bond of addition of C.
As a kind of improvement of the application electrolyte, the content of addition of C is the 0.01%～10% of the gross weight of electrolyte.
In above-mentioned addition of C, at least one in substituted or unsubstituted alkyl ether of ether compound, substituent group is halogen；And further preferred substituted or unsubstituted C1～12At least one in alkyl ether；
Alkyl ether can be cyclic ether compound, it is possible to for chain ether compound, in ether compound, the number of oxygen atom can be 1,2,3 or 4；Preferably, ether compound can be replaced by least one halogen atom, and wherein halogen atom is F, Cl, Br, preferably F.
As the object lesson of alkyl ether, can enumerate:
1-ethyoxyl-propane (referred to as EPE)；
2-trifluoromethyl-3-methoxyl group perflenapent (referred to as TMMP)；
1,1,2,2-tetra-fluoro ethyl-2', 2', 3', 3'-tetrafluoro propyl ether (F-EPE).
Preferably, the content of ether compound is the 0.01～5% of the gross weight of electrolyte, it is further preferred that the 0.1～3% of the gross weight that the content of ether compound is electrolyte.
In above-mentioned addition of C, the number of the cyano group in nitrile compound can be 1,2,3,4 or 5, for the alkane containing 1～5 cyano group, alkene containing 1～5 cyano group；It is further preferred that be the C containing 1～4 cyano group2～12Alkane, C containing 1～4 cyano group2～12Alkene.
As being mono-nitrile compound when comprising only a cyano group, it is double nitrile compounds when containing two cyano group, is three nitrile compounds when containing three cyano group, is four nitrile compounds when containing four cyano group.It addition, in described nitrile compound, carbon-carbon double bond also can be contained.Preferably, described nitrile compound be in mono-nitrile compound, double nitrile compound, three nitrile compounds and four nitrile compounds at least one.
Object lesson as nitrile compound, can enumerate: acetonitrile, propionitrile, butyronitrile, isopropyl cyanide, valeronitrile, isobutyl cyanide, 2-methylbutyronitrile, trimethylacetonitrile, own nitrile, ring valeronitrile, cyclohexanenitrile, acrylonitrile, methacrylonitrile, butene nitrile, 3-methyl butene nitrile, 2-methyl-2-butene nitrile, 2-allyl acetonitrile, 2-methyl-2-allyl acetonitrile, 3-methyl-2-allyl acetonitrile, 2-hexene nitrile, fluoride acetonitrile, two fluoride acetonitriles, trifluoro acetonitrile, 2-fluorine propionitrile, 3-fluorine propionitrile, 2, 2-difluoro propionitrile, 2, 3-difluoro propionitrile, 3, 3-difluoro propionitrile, 2, 2, 3-trifluoro propionitrile, 3, 3, 3-trifluoro propionitrile, the mono-nitrile compound such as five fluorine propionitrile；Cyanoacetyl-Cyacetazid, succinonitrile, 2-methyl succinonitrile, tetramethyl succinonitrile, glutaronitrile, 2-methyl cellosolve acetate glutaronitrile, adiponitrile, double nitrile compound such as rich horse dintrile, 2-methylene glutaronitrile etc.；Three nitrile compounds such as 1,3,5-penta trimethylsilyl nitrile, 1,2,3-the third trimethylsilyl nitrile, 1,3,6-hexane three nitrile；TCNE etc. four nitrile compound etc..
Preferably, described nitrile compound is at least one in acetonitrile, propionitrile, butyronitrile, valeronitrile, butene nitrile, 3-methyl butene nitrile, Cyanoacetyl-Cyacetazid, succinonitrile, glutaronitrile, adiponitrile (referred to as ADN) and rich horse dintrile, further preferably, described nitrile compound is selected from Cyanoacetyl-Cyacetazid, succinonitrile, glutaronitrile, adiponitrile, rich horse dintrile and 1, at least one in 3,6-hexane three nitriles.
Preferably, the described content containing nitrile compound is the 0.01～5% of the gross weight of electrolyte, it is further preferred that the 0.1～3% of the gross weight that the described content containing nitrile compound is electrolyte.
In above-mentioned addition of C, the cyclic ester compounds containing sulfur-to-oxygen double bond can be at least one in cyclic sulfates, cyclic sulfite, sultone；Wherein sultone includes saturated sultone and the sultone containing unsaturated double-bond.
Wherein, cyclic sulfates compound is as shown in formula V 1, and cyclic sulfite compound is as formula is as shown in V 3, and sultone compound is as shown in formula V 2:
Wherein, R51、R52、R53The most independent is respectively selected from substituted or unsubstituted C1～4Alkylidene, substituted or unsubstituted C2～4Alkenylene；Substituent group is selected from halogen.
Preferably, R51、R53The most independent is respectively selected from substituted or unsubstituted C1～4Alkylidene；R52Selected from substituted or unsubstituted C1～4Alkylidene, substituted or unsubstituted C2～4Alkenylene.
Preferably, the cyclic ester compounds containing sulfur-to-oxygen double bond is at least one in following compound:
Sulfuric acid vinyl ester；
Sulphuric acid propylene；
Propylene sulfite；
1,3-propane sultone (referred to as PS)；
1,4-butyl sultone；
Acrylic-1,3-sultones.
Preferably, the content of the cyclic ester compounds containing sulfur-to-oxygen double bond is the 0.01～5% of the gross weight of electrolyte, it is further preferred that the 0.1～3% of the gross weight that content is electrolyte of the cyclic ester compounds containing sulfur-to-oxygen double bond.
Cyclic ester compounds containing sulfur-to-oxygen double bond is further selected from:
Wherein, cyclic carbonate compound includes saturated cyclic carbonic ester and the cyclic carbonate containing carbon-to-carbon unsaturated bond, and its structural formula is as shown in formula V 4:
Wherein, R54Selected from substituted or unsubstituted C1～4Alkylidene, substituted or unsubstituted C2～4Alkenylene；Substituent group is selected from halogen, C2～4Thiazolinyl.
In the cyclic carbonate compound containing carbon-to-carbon unsaturated bond, carbon-to-carbon unsaturated bond is preferably double bond, and described double bond can be located on ring, it is possible to is not positioned on ring.
In above-mentioned electrolyte, it is preferable that at least one in following compound of cyclic carbonate compound:
Vinylene carbonate (referred to as VC),
Fluorinated ethylene carbonate；
Fluoro vinylene carbonate；
1,2-bis-fluoro vinylene carbonate；
Vinylethylene carbonate.
Preferably, the content of cyclic carbonate compound is the 0.01～5% of the gross weight of electrolyte, it is further preferred that the 0.1～3% of the gross weight that the content of cyclic carbonate compounds is electrolyte.
Cyclic carbonate compound is also selected from least one in following compound:
In above-mentioned addition of C, the compound containing carbon-to-nitrogen double bond is one or more in the compound containing imido grpup and the compound containing carbodiimide-based, and wherein said imido grpup is expressed asDescribed carbodiimide-based is expressed as-N=C=N-；
Compound containing carbon-to-nitrogen double bond is as shown in formula VI a；Compound containing carbodiimide-based is as shown in VI b；
R61、R62、R63、R64、R65The most independent is respectively selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl；Substituent group is selected from halogen.
As the example of the compound containing carbon-to-nitrogen double bond, can enumerate:
N-amyl group isopropylimine (referred to as NPPI),
Dicyclohexylcarbodiimide (referred to as DCC).
Preferably, the content of the compound containing carbon-to-nitrogen double bond is the 0.01～5% of the gross weight of electrolyte, it is further preferred that the 0.1～3% of the gross weight that content is electrolyte of the compound containing carbon-to-nitrogen double bond.
When additive also includes addition of C, further increase lithium ion battery cycle performance, high rate performance and high-temperature storage performance under high voltages, such as further increase lithium ion battery cycle performance and high rate performance and the high-temperature storage performance at the high voltage of 4.4V～5V and 85 DEG C under the high voltage of 4.4V～5V, in addition, further improves the security performance of lithium ion battery, such as at a temperature of 150 DEG C, the Heat stability is good of lithium ion battery, substantially without occurring smoldering, the on fire and phenomenon of blast.
In above-mentioned electrolyte, organic solvent selects non-aqueous organic solvent, such as can be selected for carbon number be 1～8 and containing the compound of at least one ester group as non-aqueous organic solvent.
Preferably, organic solvent is at least one in ethylene carbonate, Allyl carbonate, butylene, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, GBL, methyl propionate, methyl butyrate, ethyl acetate, propyl propionate, ethyl propionate and ethyl n-butyrate..Certainly the above-mentioned concrete compound being previously mentioned it is not limited only to, it is also possible to be the halogenated compound of above-mentioned concrete compound.
In above-mentioned electrolyte, described lithium salts optionally at least one in organic lithium salt or inorganic lithium salt.Especially, containing at least one in fluorine element, boron element, P elements in described lithium salts.
As the example of lithium salts, specifically can enumerate: lithium hexafluoro phosphate (LiPF6), difluorophosphate (LiPO2F2), LiBF4 (LiBF4), hexafluoroarsenate lithium (LiAsF6), lithium perchlorate (LiClO4), trifluoro sulphonyl lithium, three (trimethyl fluoride sulfonyl) lithium methide, two (trimethyl fluoride sulfonyl) imine lithium, double trifluoromethanesulfonimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), double (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) (being abbreviated as LiDFOB).
In above-mentioned electrolyte, preferably, described lithium salts is at least one in lithium hexafluoro phosphate, difluorophosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoro sulphonyl lithium, two (trimethyl fluoride sulfonyl) imine lithium, double (fluorine sulphonyl) imine lithium or three (trimethyl fluoride sulfonyl) lithium methide.
In above-mentioned electrolyte, lithium salts concentration in the electrolytic solution can be 0.5mol/L～3mol/L, it is further preferred that the concentration that lithium salts is in the electrolytic solution is 1～2mol/L.
In this application, electrolyte uses conventional method to prepare, such as by each material mix homogeneously in electrolyte.
The another object of the application is to provide a kind of lithium ion battery, including positive plate, negative plate, lithium battery diaphragm and electrolyte, wherein, the electrolyte that electrolyte provides for the application.
In above-mentioned lithium ion battery, described positive plate includes positive electrode active materials；Described negative plate includes negative active core-shell material, and wherein, described positive electrode active materials, the concrete kind of negative active core-shell material are not limited by concrete, can select according to demand.
Preferably, described positive electrode active materials is selected from cobalt acid lithium (LiCoO2), lithium-nickel-manganese-cobalt ternary material, LiFePO 4 (LiFePO4), LiMn2O4 (LiMn2O4At least one in).
Preferably, described negative active core-shell material is material with carbon element and/or silicon materials, such as native graphite, Delanium, mesophase micro-carbon ball (referred to as MCMB), hard carbon, soft carbon, silicon, silico-carbo complex, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO2, lithiumation TiO of spinel structure2-Li4Ti5O12, Li-Al alloy all can be as negative active core-shell material.
Embodiment
The application is further described below by way of instantiation.But these examples are the most 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 such as does not has special explanation, the most commercially available, and wherein used reagent also can be synthesized voluntarily by conventional synthetic method and obtains.
In following experimental example, comparative example and test example, used material is as follows:
Organic solvent: ethylene carbonate (referred to as EC), Allyl carbonate (referred to as PC), diethyl carbonate (referred to as DEC)；Lithium salts: LiPF6；
Additive:
Additive A: ester dimer；
Carbonic ester dimer: 2,5-dioxa diethylene adipate (AN1)；
Carboxylate dimer: diethylene glycol diacetate esters (AN2)；
Sultone dimer: methanesulfonic acid 4-mesyloxy-butyl ester (AN3)；
Additive B: there is the dinitrile compound of ehter bond；
Aforementioned AM1, AM2, AM3, AM4 being previously mentioned；
Addition of C:
Vinylene carbonate (VC)；
1,3-propane sultone (PS)；
Adiponitrile (ADN)；
Dicyclohexylcarbodiimide (DCC)；
Lithium battery diaphragm: 16 microns of thick polypropylene isolating membrane (model is A273, Celgard company provide).
The preparation of embodiment 1 lithium ion battery
In comparative example 1#～6#With embodiment 1～10, lithium ion battery (hereinafter referred to as battery) is prepared the most by the following method:
(1) preparation of positive plate
By cobalt acid lithium (LiCoO2), binding agent Kynoar, conductive agent acetylene black be LiCoO according to weight ratio2: Kynoar: acetylene black=96:2:2 mixes, add N-Methyl pyrrolidone (NMP), then stir under de-airing mixer effect to system and become transparent and homogeneous shape, it is thus achieved that anode sizing agent；Anode sizing agent is evenly applied on the aluminium foil that thickness is 12 μm；Aluminium foil is transferred to after room temperature is dried 120 DEG C of oven drying 1h, is then passed through colding pressing, cuts and obtain positive plate.
(2) preparation of negative plate
It is graphite by graphite, acetylene black, thickening agent sodium carboxymethyl cellulose (CMC), binding agent butadiene-styrene rubber according to weight ratio: acetylene black: binding agent butadiene-styrene rubber: sodium carboxymethyl cellulose (CMC)=95:2:2:1 mixes, after adding deionized water, under the stirring action of de-airing mixer, it is thus achieved that cathode size；Cathode size is coated uniformly on Copper Foil；Copper Foil is transferred to after room temperature is dried 120 DEG C of oven drying 1h, is then passed through colding pressing, cuts and obtain negative plate.
(3) preparation of electrolyte
Comparative example 1#～6#It is prepared the most by the following method with electrolyte used in embodiment 1～10:
In water content < in the argon gas atmosphere glove box of 10ppm, EC, PC and DEC mix homogeneously is formed organic solvent, the lithium salts being fully dried is dissolved in above-mentioned mixed organic solvents, add ester dimer compound or ester dimer compound and additive B the most in organic solvent, mix homogeneously, it is thus achieved that electrolyte.Wherein, the concentration of lithium salts is 1mol/L, and the weight ratio of EC, PC, DEC is EC:PC:DEC=1:1:2.
(4) preparation of lithium ion battery
Positive plate, lithium battery isolation membrane, negative plate being folded in order, make lithium battery isolation membrane be between positive and 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, through Vacuum Package, stand, be melted into, the operation such as shaping, it is thus achieved that battery.
In the preparation process of above-mentioned battery, the concrete kind of additive used in electrolyte selected in each battery, each electrolyte and content thereof, as shown in Table 1 below, the content of described additive is the calculated percetage by weight of gross weight based on electrolyte.
Table 1
Note: in table 1 above, " " represents without this corresponding in the table material.
Test case
(1) the cycle performance test of battery
By comparative example 1#～6#Following test is all carried out with the battery obtained in embodiment 1～10:
At a temperature of 45 DEG C, with the multiplying power of 0.5C by constant-current charging of battery to 4.45V, then constant-voltage charge to electric current is 0.05C, then with 0.5C constant current discharge to 3.0V, above-mentioned charging and discharging is a circulation, charging and discharging so it is repeated, respectively by following formula be calculated circulating battery 50 times, capability retention after 100 times and 300 times.It addition, the capability retention of each battery is as shown in Table 2 below.
The capability retention of n-th circulation=(discharge capacity of the discharge capacity/circulate first of n-th circulation) × 100%.
(2) the high rate performance test of battery
By comparative example 1#～6#Following test is all carried out with the battery obtained in embodiment 1～10:
By battery with 0.5C constant-current discharge to 3.0V, shelve 5min, then with 0.5C constant-current charge to 4.45V, and constant-voltage charge, be 0.05C by electric current, stand 5min, more respectively with 0.2C, 1C, 1.5C, 2C constant-current discharge to by voltage 3.0V.Discharge capacity under the conditions of record 0.2C, 1C, 1.5C, 2C is D1, discharge capacity under record 0.2C is D0, and based on the discharge capacity under 0.2C, it is calculated battery discharge capacitance under different multiplying by following formula and (surveys 15 batteries, take its meansigma methods), then the high rate performance of battery is characterized by battery discharge capacitance under different multiplying.It addition, the discharge capacitance that each battery is under different multiplying is as shown in Table 2 below.
The discharge capacitance of battery=[(D1-D0)/D0] × 100%
(3) the high-temperature storage performance test of battery
By comparative example 1#～6#Following test is all carried out with the battery obtained in embodiment 1～10:
At 25 DEG C, with the electric current of 0.5C by constant-current charging of battery to 4.45V, again with 4.45V constant-voltage charge to electric current as 0.025C, battery is made to be in 4.45V fully charged state, now detecting the thickness obtained is the thickness before battery storage, stores 4 hours the most respectively, stores 30 days at 60 DEG C, under the conditions of above-mentioned two after storage at 85 DEG C, thickness after detection obtains battery storage respectively, then calculates the thickness swelling of the battery after storage at different conditions by following formula.It addition, each battery store at different conditions after thickness swelling as shown in Table 2 below.
The thickness swelling of battery=[thickness before (thickness before thickness-storage after storage)/storage] × 100%
Table 2
(4) hot tank test
By comparative example 1#～6#Following test is all carried out with the battery obtained in embodiment 1～10:
1) with 1.0C electric current constant current, battery being charged to 4.45V, then constant-voltage charge to electric current is down to 0.05C, and charging stops；
2) battery is placed in hot tank, start to warm up to 150 DEG C from 25 DEG C with the programming rate of 5 DEG C/min, remain temperature-resistant after arriving 150 DEG C, then timing is started, observe the state of battery after 1h, by the standard of this test be: battery is without smoldering, without on fire, without blast, the most often 5 batteries of group.The result of the hot tank test of each battery is as shown in table 3.
Tested by above-mentioned hot tank, characterize the safety of battery.
Table 3
Related data from above-mentioned table 2, table 3 is appreciated that, compared with the battery prepared in comparative example, the battery prepared by embodiment, capability retention, the high rate performance under 1C, 1.5C, 2C and the thermostability at 150 DEG C lifting the most by a relatively large margin after circulation at 45 DEG C, and the thickness swelling at 60 DEG C and 85 DEG C significantly reduces.
Thus it is appreciated that: owing to electrolyte includes ester dimer and has the dintrile of ehter bond; both can form the SEI film of stable and uniform on both positive and negative polarity surface; it is effectively increased battery cycle performance under high voltages and high rate performance; there is the dintrile of ehter bond have precedence over ester dimer and form reticular protection film at positive pole; and the film forming of ester dimer is had inducing action; the two cooperatively forms the composite protection film of stable densification, and this composite protection film at high temperature or has high stability, Low ESR under high pressure.Especially when embodiment 11～14 carbonic ester dimer or carboxylate dimer and the combination of sultone dimer, effect becomes apparent from, this is that the composite S EI membrane structure owing to being formed is stable, good stability in the circulating cycle, along with the carrying out of circulation is less likely to occur repeatedly to decompose and is again formed, to improving, battery cycle performance effect under high voltages is the most obvious.
When additive also includes addition of C, the cycle performance of battery can be improved further, such as under the high pressure of 4.45V～4.5V after repeatedly circulation, still there is higher capability retention, in addition it is possible to improve battery high rate performance, high-temperature storage performance and security performance under high voltages further.
Embodiment 2
Preparing electrolyte and lithium ion battery according to the method for embodiment 1, difference is, in electrolyte, the composition of additive is as shown in table 4；
Table 4
Lithium ion battery prepared by the electrolyte of employing table 4, and the character of preparation-obtained battery is similar to Example 1, repeats no more as space is limited.
The announcement of book according to the above description, the application those skilled in the art can also carry out suitable change and amendment to above-mentioned embodiment.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, including lithium salts, organic solvent and additive, it is characterized in that, containing additive A and additive B in described additive, at least one in dimer ester compounds of described additive A, described dimer ester compounds includes carbonic ester dimer, carboxylate dimer and sultone dimer；At least one in the dinitrile compound with ehter bond of described additive B.
Electrolyte the most according to claim 1, it is characterised in that the structural formula of described carbonic ester dimer is as shown in formula I, and described carboxylate dimer structure formula is as shown in formula II:
In formula I, R11、R13The most independent is respectively selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted C2～12Alkynyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C5～22Heterocyclic base；Substituent group is selected from halogen, C6～26Aryl, C3～8Cycloalkyl；
R12Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C6～26Arlydene, by least one ehter bond and at least one substituted or unsubstituted C1～12The group of alkylidene composition, substituent group is selected from halogen；
In formula II, R21、R23The most independent is respectively selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted C2～12Alkynyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C5～22Heterocyclic base；Substituent group is selected from halogen, C6～26Aryl, C3～8Cycloalkyl；
R22Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C6～26Arlydene, by least one ehter bond and at least one substituted or unsubstituted C1～12The group of alkylidene composition, substituent group is selected from halogen.
Electrolyte the most according to claim 1, it is characterised in that described sultone dimer structure formula is as shown in formula III:
In formula III, R31、R33The most independent is respectively selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted C2～12Alkynyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C5～22Heterocyclic base；Substituent group is selected from halogen, C6～26Aryl, C3～8Cycloalkyl；
R32Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C6～26Arlydene, by least one ehter bond and at least one substituted or unsubstituted C1～12The group of alkylidene composition, substituent group is selected from halogen.
Electrolyte the most according to claim 1, it is characterised in that described in there is the structural formula of dinitrile compound of ehter bond as shown in formula IV:
R41、R42、R43The most independent is respectively selected from C1～5Alkylidene, C2～5Alkenylene, m is the integer of 1～5.
Electrolyte the most according to claim 1, it is characterized in that, described have the dinitrile compound of ehter bond selected from 3, 5-dioxa-pimelic dinitrile, 1, 4-bis-(2-cyanoethoxy) butane, ethylene glycol bisthioglycolate (2-cyano ethyl) ether, diethylene glycol two (2-cyano ethyl) ether, triethylene glycol two (2-cyano ethyl) ether, TEG two (2-cyano ethyl) ether, 1, 3-bis-(2-cyanoethoxy) propane, 1, 4-bis-(2-cyanoethoxy) butane, 1, 5-bis-(2-cyanoethoxy) pentane, at least one in ethylene glycol bisthioglycolate (4-cyanobutyl) ether.
Electrolyte the most according to claim 1, it is characterised in that the total content of described additive A and additive B is the 0.01%～10% of the gross weight of electrolyte.
Electrolyte the most according to claim 1, it is characterized in that, described additive also includes addition of C, at least one in ether compound, nitrile compound, cyclic ester compounds containing sulfur-to-oxygen double bond, cyclic carbonate compound, compound containing carbon-to-nitrogen double bond of described addition of C；
At least one in substituted or unsubstituted alkyl ether of described ether compound, substituent group is halogen；
Described nitrile compound is selected from the alkane containing 1～5 cyano group, the alkene containing 1～5 cyano group at least one；
At least one in cyclic sulfates, cyclic sulfite, sultone of the described cyclic ester compounds containing sulfur-to-oxygen double bond；
The described compound containing carbon-to-nitrogen double bond is for selected from containingAt least one in the compound of-N=C=N-.
Electrolyte the most according to claim 7, it is characterised in that
Described ether compound is selected from substituted or unsubstituted C1～12At least one in alkyl ether, substituent group is halogen；
Described nitrile compound is selected from the C containing 1～4 cyano group2～12Alkane, C containing 1～4 cyano group2～12In alkene at least one；
At least one in the compound shown in formula V 1, formula V 2, formula V 3 of the described cyclic ester compounds containing sulfur-to-oxygen double bond: as described at least one in compound as shown in formula V 4 of cyclic carbonate compound:
R51、R52、R53、R54The most independent is respectively selected from substituted or unsubstituted C1～4Alkylidene, substituted or unsubstituted C2～4Alkenylene；Substituent group is selected from halogen, C2～4Thiazolinyl.
Electrolyte the most according to claim 7, it is characterized in that, described addition of C is selected from 1-ethyoxyl-propane, 2-trifluoromethyl-3-methoxyl group perflenapent, 1, 1, 2, 2-tetra-fluoro ethyl-2', 2', 3', 3'-tetrafluoro propyl ether, acetonitrile, propionitrile, butyronitrile, valeronitrile, butene nitrile, 3-methyl butene nitrile, Cyanoacetyl-Cyacetazid, succinonitrile, glutaronitrile, adiponitrile, rich horse dintrile, sulfuric acid vinyl ester, sulphuric acid propylene, propylene sulfite, 1, 3-N-morpholinopropanesulfonic acid lactone, 1, 4-butyl sultone, acrylic-1, 3-sultones, vinylene carbonate, fluorinated ethylene carbonate, fluoro vinylene carbonate, 1, 2-bis-fluoro vinylene carbonate, vinylethylene carbonate, at least one in dicyclohexylcarbodiimide；
It is furthermore preferred that the 0.01%～10% of the gross weight that the content of described addition of C is electrolyte.
10. a lithium ion battery, it is characterised in that include the positive plate containing positive electrode active materials, negative plate containing negative active core-shell material, lithium battery diaphragm and the electrolyte according to any one of claim 1～9.
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| WO2020119808A1 (en) * | 2018-12-14 | 2020-06-18 | 宁德时代新能源科技股份有限公司 | Electrolyte, battery and device |
| CN110335991B (en) * | 2019-07-15 | 2021-04-13 | 骆驼集团武汉光谷研发中心有限公司 | Long-cycle-life battery and manufacturing method thereof |
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| CN110416614A (en) * | 2019-08-02 | 2019-11-05 | 湖州昆仑动力电池材料有限公司 | A kind of nickelic electrolyte for lithium ion battery |
| CN112786963A (en) * | 2019-11-01 | 2021-05-11 | 广州汽车集团股份有限公司 | Lithium ion battery electrolyte, preparation method thereof, lithium ion battery cell, lithium ion battery pack and application thereof |
| CN112786963B (en) * | 2019-11-01 | 2022-03-11 | 广汽埃安新能源汽车有限公司 | Lithium ion battery electrolyte, preparation method thereof, lithium ion battery cell, lithium ion battery pack and application thereof |
| WO2021128000A1 (en) * | 2019-12-24 | 2021-07-01 | 宁德时代新能源科技股份有限公司 | Secondary battery and device containing secondary battery |
| CN111129598A (en) * | 2019-12-30 | 2020-05-08 | 东莞市杉杉电池材料有限公司 | High-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery thereof |
| CN112400249A (en) * | 2020-03-24 | 2021-02-23 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
| US11961961B2 (en) | 2022-04-27 | 2024-04-16 | Contemporary Amperex Technology Co., Limited | Secondary battery and apparatus containing the same |
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