CN105932332A - Electrolytic solution and lithium-ion battery comprising same - Google Patents
Electrolytic solution and lithium-ion battery comprising same Download PDFInfo
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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
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- 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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Abstract
The invention relates to the field of batteries, in particular to an electrolytic solution and a lithium-ion battery comprising the same. The electrolytic solution comprises an electrolyte, a solvent and an additive, wherein the additive comprises a sulfonate cyclic quaternary ammonium salt and a sultone compound. When the electrolytic solution contains the sulfonate cyclic quaternary ammonium salt and the sultone compound, the sulfonate cyclic quaternary ammonium salt and the sultone compound can be decomposed on the positive electrode surface and the negative electrode surface to form a thick film which stable performance; and continuous oxidation and reduction reaction of the electrolytic solution on the positive electrode surface and the negative electrode surface at a high temperature are avoided, so that decomposition of the electrolytic solution and internal resistance rise of the lithium-ion battery are weakened; and the cycle performance of the lithium-ion battery at the high temperature is improved.
Description
Technical field
The application relates to field of batteries, specifically, relates to a kind of electrolyte and includes the lithium ion battery of this electrolyte.
Background technology
In recent years, along with developing rapidly that lithium ion battery is applied in portable electronics field, people are to portable for these
Formula electronic equipment provides the demand of small-sized, light, the thin and high performance battery of power supply day by day to increase.Due to the high energy to battery
The continuous pursuit of metric density, using the both positive and negative polarity of high compacted density or the poor negative material of high power capacity cycle performance is current work
A kind of strategy that industry is commonly used.The problem brought therewith is that electrolyte cannot fully infiltrate electrode, causes the charging of battery
Platform raises and discharge platform reduces the output performance affecting battery.When low-temperature circulating, owing to the dynamic performance of battery is owed
Good, easily analyse lithium during low temperature discharge and recharge.
Being analyzed the problems referred to above, battery electrode surface when chemical conversion can generate one layer of SEI film (solid electrolyte film),
This layer of solid electrolyte film controls the passage of ion turnover, is to control the dynamic (dynamical) key factor of electrode reaction.Low
Under temperature environment, if the SEI film formed is the thickest, membrane impedance is higher, then lithium ion cannot migrate through, and will occur to analyse lithium.Another
At high temperature, the SEI film of generation is the most form compact and stable for aspect, then SEI film can gradually dissolve or rupture, and causes the negative pole exposed to continue
Continue and react with electrolyte, while consuming electrolyte so that battery capacity reduces.
It addition, controlling another factor of battery high temperature performance is the electrolyte wetting capacity to pole piece, if increasing eutectic
Point, low viscosity solvent content, the cryogenic property of battery increases really, but its high-temperature behavior can be deteriorated, and both cannot take into account.
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 including this electrolyte.
In order to complete the purpose of the application, the technical scheme of employing is:
The application relates to a kind of electrolyte, and described electrolyte includes that electrolyte, solvent and additive, described additive include
Sulphonic acid ester cyclic quaternary ammonium salts and sultone compounds.
Preferably, the structural formula of described sulphonic acid ester cyclic quaternary ammonium salts is as shown in formula I:
In formula I, R11Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, replacement or not
Substituted C2～12Alkynyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted C1～12Acyloxy；
R12Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C2～12Alkenylene, replacement or unsubstituted
C2～12Alkynylene, substituted or unsubstituted C1～12Alkylene acyl group；
R13Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted
C2～12Alkynyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted C1～12Acyloxy, substituted or unsubstituted C6～22
Aryl, substituted or unsubstituted C5～22Heterocyclic base；
R14Selected from substituted or unsubstituted C1～3Alkylidene；
Substituent is selected from cyano group, halogen；
X-Represent anion.
Preferably, R11、R13The most independent is respectively selected from substituted or unsubstituted C1～6Alkyl, R12Selected from replacing or not taking
The C in generation1～12Alkylidene, R14Selected from substituted or unsubstituted C1～2Alkylidene.
Preferably, the cation group of described sulphonic acid ester cyclic quaternary ammonium salts is selected from following structural formula:
Preferably, the anion X of described sulphonic acid ester cyclic quaternary ammonium salts—Selected from following group:
F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、(FSO2)2N-、
Preferably, described sultone compounds selected from as in Formula II A, Formula II B, Formula II C or Formula II D compound at least
A kind of；
Wherein, R21、R22、R23、R24Be respectively selected from independently of one another hydrogen atom, halogen, nitro, cyano group, carboxyl, sulfonic group,
Substituted or unsubstituted C1～20Alkyl, substituted or unsubstituted C2～20Thiazolinyl, substituted or unsubstituted C2～20Alkynyl, replacement or not
Substituted C1～20Alkoxyl, substituted or unsubstituted C1～20Alkanoyl, substituted or unsubstituted C1～20Alkane ether；Substituent is selected from
Halogen, nitro, cyano group, carboxyl or sulfonic group.
Preferably, described sultone compounds is selected from such as Formula II A ', Formula II B ', in Formula II C ' or Formula II D ' compound
At least one；
Wherein, R21’、R22’、R23’、R24' it is respectively selected from substituted or unsubstituted C independently of one another1～6Straight or branched alkane
Base, substituted or unsubstituted C5～7Cycloalkyl, substituted or unsubstituted C2～6Thiazolinyl, substituted or unsubstituted C2～6Alkynyl, replaces
Base is selected from halogen or cyano group.
Preferably, described sulphonic acid ester cyclic quaternary ammonium salts mass percent in the electrolytic solution is 0.1%～10%, is preferably
1%～6%；Described sultone compounds mass percent in the electrolytic solution is 0.1%～10%, preferably 1%～
6%.
Preferably, at least one in chain ester or cyclic ester of described solvent, described chain ester is selected from carbonic acid diformazan
Ester, diethyl carbonate, methyl ethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl formate, Ethyl formate, methyl acetate, second
In acetoacetic ester, propyl propionate, ethyl butyrate, ethyl propionate, propyl butyrate at least one or several, described cyclic ester be selected from carbon
Vinyl acetate, propene carbonate, butylene, vinylene carbonate, ethylene sulfite, propylene sulfite, γ-Ding Nei
At least one in ester, oxolane.
Preferably, described electrolyte include described electrolyte for selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate,
Hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate, LiN (SO2Rf)2、LiN(SO2F)(SO2Rf), double trifluoromethanesulfonimide lithium, double
At least one in (fluorine sulphonyl) imine lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, wherein, Rf=CnF2n+ 1, n are 1
～the integer of 10, preferably lithium hexafluoro phosphate or LiN (SO2Rf)2。
The application further relates to a kind of lithium ion battery, including the positive plate containing positive electrode active materials, containing negative electrode active
The electrolyte of the negative plate of material, barrier film and the application.
The technical scheme of the application at least has a following beneficial effect:
The application finds, when in electrolyte containing sulphonic acid ester cyclic quaternary ammonium salts and sultone compounds, it is positive and negative
Equal decomposable asymmetric choice net on surface, pole and form stable performance and abundant film, and extend this film existence time at high temperature, due to this
Film can reduce contacting of positive and negative electrode and electrolyte, thus avoid electrolyte under high temperature occur on positive and negative electrode surface continued oxidation and
Reduction reaction, and then reduce the decomposition of electrolyte and the internal resistance rising of lithium ion battery, improve lithium ion battery at high temperature
Under cycle performance.Such as lithium ion battery has the cycle performance of excellence under 4.6V high voltage and at 45 DEG C, at 85 DEG C
There is excellent storage performance.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic resonance map of compound A；
Fig. 2 is the nuclear magnetic resonance map of compound B.
Detailed description of the invention
Being described in detail below by the application, the feature of the application and advantage will become more along with these explanations
For clear, clear and definite.
The purpose of the application is to provide a kind of electrolyte, and including solvent, electrolyte and additive, described additive includes
Sulphonic acid ester cyclic quaternary ammonium salts and sultone compounds.
In above-mentioned electrolyte, described sultones can be saturated sultones, it is possible to for unsaturated sulfonic acid lactone.
As a kind of improvement of the application electrolyte, the structural formula such as formula of the sulphonic acid ester cyclic quaternary ammonium salts that the application is used
Shown in 1:
In formula I, R11Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, replacement or not
Substituted C2～12Alkynyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted C1～12Acyloxy；
R12Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C2～12Alkenylene, replacement or unsubstituted
C2～12Alkynylene, substituted or unsubstituted C1～12Alkylene acyl group；
R13Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted
C2～12Alkynyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted C1～12Acyloxy, substituted or unsubstituted C6～22
Aryl, substituted or unsubstituted C5～22Heterocyclic base；
R14Selected from substituted or unsubstituted C1～3Alkylidene；
Substituent is selected from cyano group, halogen；
X-Represent anion.
In the formula of the application:
Carbon number is the alkyl of 1～12, and alkyl can be chain-like alkyl, it is possible to for cycloalkyl, be positioned on the ring of cycloalkyl
Hydrogen can be replaced by alkyl, in described alkyl, the preferred lower limit of carbon number is 2,3,4,5, preferred higher limit is 3,4,5,
6,8,10.Preferably, the alkyl selecting carbon number to be 1～10, it is further preferred that the chain selecting carbon number to be 1～6
Alkyl, carbon number is the cycloalkyl of 3～8, it is further preferred that the chain-like alkyl selecting carbon number to be 1～4, carbon is former
Subnumber is the cycloalkyl of 5～7.As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, positive fourth
Base, 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.
When in the alkyl that the aforementioned carbon number being previously mentioned is 1～12 containing oxygen atom, it can be alkoxyl.Preferably,
The alkoxyl selecting carbon number to be 1～10, it is further preferred that the alkoxyl selecting carbon number to be 1～6, further
Preferably, the alkoxyl selecting carbon number to be 1～4.As the example of alkoxyl, specifically can enumerate: methoxyl group, ethoxy
Base, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, ring
Hexyloxy.
When in the alkyl that the aforementioned carbon number being previously mentioned is 1～12 containing oxygen atom, it can be also acyloxy.Preferably
Ground, the acyloxy selecting carbon number to be 1～10, it is further preferred that the acyloxy selecting carbon number to be 1～6, more enters one
Preferably, selection carbon number is the acyloxy of 1～4 to step.As the example of acyloxy, specifically can enumerate: formyloxy, second
Acyloxy, positive propionyloxy, isopropenoxy, positive butyryl acyloxy, secondary butyryl acyloxy, tertiary butyryl acyloxy, positive valeryl epoxide, isoamyl
Acyloxy.
Carbon number be the thiazolinyl of 2～12 can be cyclic alkenyl radical, it is possible to for chain thiazolinyl.It addition, in thiazolinyl double bond
Number is preferably 1.In described thiazolinyl, the preferred lower limit of carbon number is 3,4,5, and preferred higher limit is 3,4,5,6,8,10.
Preferably, the thiazolinyl selecting carbon number to be 2～10, it is further preferred that the thiazolinyl selecting carbon number to be 2～6, more enters one
Preferably, selection carbon number is the thiazolinyl of 2～5 to step.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 2～12 be straight or branched alkylidene, in described alkylidene, carbon number is preferred
Lower limit is 2,3,4,5, and preferred higher limit is 3,4,5,6,8,10.Preferably, the alkylidene selecting carbon number to be 1～6.
As the example of alkyl, specifically can enumerate: methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, Asia
Sec-butyl, pentylidene, hexylidene.
Carbon number be the alkenylene of 2～6 be straight or branched alkenylene, in thiazolinyl, the number of double bond is preferably 1.Institute
Stating the preferred lower limit of carbon number in alkenylene is 3,4,5, and preferred higher limit is 3,4,5,6,8,10.Preferably, select
Carbon number is the alkenylene of 2～6.As the example of alkenylene, specifically can enumerate: ethenylidene, acrol, sub-isopropyl
Thiazolinyl, sub-alkene butyl, sub-alkene amyl group.Specifically chosen identical with alkenylene to alkynylene.
Carbon number is the aryl of 6～22, such as phenyl, benzene alkyl, at least contain a phenyl aryl such as xenyl,
Condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base also can be replaced by alkyl or thiazolinyl.Preferably, choosing
Select the aryl that carbon number is 6～16, it is further preferred that the aryl selecting carbon number to be 6～14, the most preferably
Ground, the aryl selecting carbon number to be 6～9.As the example of aryl, specifically can enumerate: phenyl, benzyl, xenyl, to first
Phenyl, o-tolyl, a tolyl.
Carbon number is the heterocyclic base of 5～22, is selected from: furyl, thienyl, pyrrole radicals, thiazolyl, imidazole radicals, pyrrole
Piperidinyl, pyrazinyl, pyrimidine radicals, pyridazinyl, indyl, quinolyl etc..
A kind of improvement as the application electrolyte: R11Selected from substituted or unsubstituted C1～6Alkyl, replacement or unsubstituted
C2～6Thiazolinyl, substituted or unsubstituted C2～6Alkynyl, substituted or unsubstituted C1～6Alkoxyl, substituted or unsubstituted C1～6Acyl
Epoxide；
R12Selected from substituted or unsubstituted C1～6Alkylidene, substituted or unsubstituted C2～6Alkenylene, substituted or unsubstituted
C2～6Alkynylene, substituted or unsubstituted C1～6Alkylene acyl group；
R13Selected from substituted or unsubstituted C1～6Alkyl, substituted or unsubstituted C1～6Alkoxyl, substituted or unsubstituted
C1～6Acyloxy, substituted or unsubstituted phenyl, substituted or unsubstituted pyridine radicals；
R14Selected from substituted or unsubstituted C1～2Alkylidene；
Substituent is cyano group, halogen；
X-Represent anion.
As a kind of improvement of the application electrolyte, R11Selected from substituted or unsubstituted C1～6Alkyl；R12Selected from replace or
Unsubstituted C1～12Alkylidene；R13Selected from substituted or unsubstituted C1～6Alkyl；R14Selected from substituted or unsubstituted C1～2Alkylene
Base.
As a kind of improvement of the application electrolyte, R11Selected from C1～6Alkyl；R12Selected from C1～12Alkylidene；R13Selected from replacing
Or unsubstituted C1～6Alkyl；R14Selected from C1～2Alkylidene.
As a kind of improvement of the application electrolyte, the cation group of sulphonic acid ester cyclic quaternary ammonium salts is selected from following structure
Formula:
As a kind of improvement of the application electrolyte, the cation group of sulphonic acid ester cyclic quaternary ammonium salts is also selected from following
Structural formula:
As a kind of improvement of the application electrolyte, the anion X of sulphonic acid ester cyclic quaternary ammonium salts—Selected from following group:
F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、(FSO2)2N-、
As the example of sulphonic acid ester cyclic quaternary ammonium salts, specific as follows shown:
As a kind of improvement of the application electrolyte, sultone compounds is selected from such as Formula II A, Formula II B, Formula II C or formula
At least one in IID compound；
Wherein, R21、R22、R23、R24Be respectively selected from independently of one another hydrogen atom, halogen, nitro, cyano group, carboxyl, sulfonic group,
Substituted or unsubstituted C1～20Alkyl, substituted or unsubstituted C2～20Thiazolinyl, substituted or unsubstituted C2～20Alkynyl, replacement or not
Substituted C1～20Alkoxyl, substituted or unsubstituted C1～20Alkanoyl, substituted or unsubstituted C1～20Alkane ether；Substituent is selected from
Halogen, nitro, cyano group, carboxyl or sulfonic group.
As a kind of improvement of the application electrolyte, sultone compounds is selected from such as Formula II A ', Formula II B ', Formula II C ' or
Formula II D ' at least one in compound；
Wherein, R21’、R22’、R23’、R24' it is respectively selected from substituted or unsubstituted C independently of one another1～6Straight or branched alkane
Base, substituted or unsubstituted C5～7Cycloalkyl, substituted or unsubstituted C2～6Thiazolinyl, substituted or unsubstituted C2～6Alkynyl, replaces
Base is selected from halogen or cyano group.
In this application, halogen is F, Cl, Br.
In above-mentioned chemical formula, substituent is as described below.
Carbon number is the alkyl of 1～20, can be chain-like alkyl, it is possible to for cycloalkyl, be positioned at the ring hydrogen of cycloalkyl
Can be replaced by alkyl.In alkyl, the preferred lower limit of carbon number is 2,3,4,5, and preferred higher limit is 3,4,5,6,8,10,
12,14,16,18.Preferably, the alkyl selecting carbon number to be 1～10, it is further preferred that selecting carbon number is 1～6
Chain-like alkyl, carbon number is the cycloalkyl of 3～8, it is further preferred that select carbon number be 1～4 chain alkane
Base, carbon number is the cycloalkyl of 5～7.As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl
Base, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, cyclopenta, cyclohexyl.
Carbon number be 2～20 thiazolinyls, carbon number be that in 2～20 alkynyls, in thiazolinyl, the number of double bond is preferably 1,
The number of three keys in alkynyl is preferably 1.The preferred lower limit of carbon number of alkenyl or alkynyl is 3,4,5, preferably on
Limit value is 3,4,5,6,8,10,12,14,16,18.Preferably, select carbon number be 2～10 thiazolinyl, carbon number be 2～
The alkynyl of 10, it is further preferred that the alkynyl that the thiazolinyl selecting carbon number to be 2～6, carbon number are 2～6, further
Preferably, the thiazolinyl, the carbon number that select carbon number to be 2～5 are the alkynyl of 2～5.
As the example of unsaturated alkyl, specifically can enumerate: vinyl, pi-allyl, isopropenyl, pentenyl, hexamethylene
Thiazolinyl, cycloheptenyl, cyclo-octene base, propinyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-methyl isophthalic acid-propinyl, 2-first
Base-3-propinyl, pentynyl, 1-hexin base, 3-methyl isophthalic acid-butynyl, 3,3-dimethyl-1-butynyl, heptynyl, octyne
Base.
When in the alkyl that the aforementioned carbon number being previously mentioned is 1～20 containing oxygen atom time, can be carbon number be 1～20
Alkoxyl or saturated fat ether that carbon number is 2～20.Preferably, alkoxyl, the carbon selecting carbon number to be 1～10
Atomicity is the saturated fat ether of 1～10, it is further preferred that the alkoxyl, the carbon number that select carbon number to be 1～6
It is the saturated fat ether of 1～6, it is further preferred that the alkoxyl selecting carbon number to be 1～4, carbon number are 1～4
Saturated fat ether.As the example of oxy radical, specifically can enumerate: methoxyl group, ethyoxyl, positive propoxy, isopropyl oxygen
Base, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, cyclohexyloxy, methoxy,
Ethoxyethyl group, isopropoxy normal-butyl.
After the alkyl that the carbon number being previously mentioned is 1～20 is replaced by halogen atom, the corresponding carbon number that formed is 1
～the haloalkyl of 20, wherein halogen atom is F, Cl, Br.In the halo group formed, halogen atom to part hydrogen atom or
The whole hydrogen atom of person replaces, and such as, the number of halogen atom can be 1,2,3 or 4.
Preferably, the haloalkyl selecting carbon number to be 1～10, it is further preferred that selecting carbon number is 1～6
Halo chain-like alkyl, carbon number be the halogenated cycloalkyl of 3～8, it is further preferred that selecting carbon number is 1～4
Halo chain-like alkyl, carbon number are the halogenated cycloalkyl of 5～7.As the example of haloalkyl, specifically can enumerate: trifluoro
Methyl (-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-fluorine cyclopenta, 1-fluoro-3-methylcyclohexyl, wherein F can be replaced by Cl and/or Br.
After the alkyl that the carbon number being previously mentioned is 1～20 is replaced by cyano group, corresponding formed carbon number be 2～
The alkane cyano group of 21, wherein cyano group can to the part hydrogen atom in abovementioned alkyl or all hydrogen atom replace, cyano group
Number is preferably 1.
Preferably, the alkane cyano group selecting carbon number to be 2～10, it is further preferred that selecting carbon number is 2～6
Chain alkane cyano group, carbon number are the cycloalkanes cyano group of 4～8, it is further preferred that the chain alkane selecting carbon number to be 3～5
Cyano group, carbon number are the cycloalkanes cyano group of 4～7.As the example of the group containing cyano group, specifically can enumerate: cyanogen methyl, 2-
Cyano ethyl, 3-cyano group n-pro-pyl, 2-cyanoisopropyl, 4-cyano group normal-butyl, 4-cyano group isopentyl, 6-cyano group n-hexyl, 3-
Cyan cyclopentyl, 4-cyanogen methylcyclohexyl.
After the alkyl that the carbon number being previously mentioned is 1～20 is replaced by nitro, carboxyl or sulfonic group, formed accordingly
4-nitro alkyl, carboxyalkyl, sulfonic group alkyl, wherein nitro, carboxyl or sulfonic group are to part hydrogen atom or whole hydrogen atom
Replacing, such as, substituted number can be 1,2,3 or 4.After alkyl is replaced by above-mentioned group, can be formed as follows
Group: nitre methyl, 2-nitro-ethyl, 3-nitro n-pro-pyl, 2-nitro isopropyl, 4-nitro normal-butyl, 4-nitro isopentyl, 6-
Nitro n-hexyl, 3-nitro cyclopenta, 4-nitre methylcyclohexyl etc., in the example enumerated, nitro can be by carboxyl or sulfonic group
Replaced.
As the example of sultones, shown in table 1 specific as follows:
Table 1
As the example of sultones, it is further selected from least one in following compound:
As a kind of improvement of the application electrolyte, the content of sulphonic acid ester cyclic quaternary ammonium salts is the gross weight of electrolyte
0.1%～10%, preferably the 1%～6% of the gross weight of electrolyte；The content of sultone compounds is the gross weight of electrolyte
The 0.1%～10% of amount, preferably the 1%～6% of the gross weight of electrolyte.
If the content of sulphonic acid ester cyclic quaternary ammonium salts or sultone compounds is excessive in electrolyte, then can be at positive and negative plate
Surface forms the thicker and passivating film of densification, reduces the conductive performance of lithium ion, thus deteriorates lithium ion battery at high temperature
Cycle performance.
If sulphonic acid ester cyclic quaternary ammonium salts or sultone compounds content are too small in the electrolytic solution, it is impossible to be effectively improved lithium from
The storage performance at high temperature of sub-battery and cycle performance.
In above-mentioned electrolyte, described nonaqueous solvents is selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), carbonic acid first
Ethyl ester (EMC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), methyl formate (MF), Ethyl formate (EF), methyl acetate
(MA), the one in ethyl acetate (EA), propyl propionate (PP), ethyl butyrate (EB), ethyl propionate (EP), propyl butyrate (PB)
Or it is several, also including but not limited to following cyclic ester such as ethylene carbonate (EC), propene carbonate (PC), butylene
(BC), vinylene carbonate (VC), ethylene sulfite (ES), propylene sulfite (PS), gamma-butyrolacton (BL), tetrahydrochysene furan
Mutter at least one in (THF).Additionally, nonaqueous solvents can also enumerate ionic liquid etc..It addition, for used herein
Nonaqueous solvents, can be used alone one, it is also possible to according to purposes in any combination, ratio be used in mixed way two or more.Its
In, from for its redox electrochemical stability with react the viewpoint of relevant chemical stability to solute hot, above-mentioned and examine
Consider, particularly preferably propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate.
In above-mentioned electrolyte, described electrolyte can be organic bath, it is possible to for inorganic electrolyte, specifically, institute
State and electrolyte can contain at least one in fluorine element, boron element, P elements.Preferably, described electrolyte is selected from hexafluoro phosphorus
Acid lithium (LiPF6), LiBF4 (LiBF4), lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), tetrafluoro oxalic acid phosphoric acid
Lithium (LiTFOP), LiN (SO2Rf)2、LiN(SO2F)(SO2Rf), double trifluoromethanesulfonimide lithium LiN (CF3SO2)2(it is abbreviated as
LiTFSI), double (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (being abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2(it is 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, and 2n+1 more than zero integer.Particularly preferably LiPF6And/or LiN
(SO2Rf)2.Described electrolyte concentration in the electrolytic solution is 0.5M～2M (M=mol L-1)。
In this application, the preparation method of electrolyte selects conventional method, such as can by organic solvent, electrolyte and
Additive mixes.
The another object of the application there are provided lithium ion battery, and described lithium ion battery includes electrolyte, containing just
The positive plate of pole active material, the negative plate containing negative active core-shell material and barrier film.
In above-mentioned lithium ion battery, described positive plate also includes binding agent and conductive agent, will include positive-active material
The anode sizing agent of material, binding agent and conductive agent is coated on plus plate current-collecting body, treats that anode sizing agent obtains positive plate after drying.Equally
, the cathode size including negative active core-shell material, binding agent and conductive agent is coated on negative current collector, treats cathode size
Obtain negative plate after drying.
Preferably, described positive electrode active materials is selected from cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material, ferrous phosphate
Lithium, LiFePO4 (LiFePO4), LiMn2O4 (LiMnO2At least one in), such as cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material
Mixture can be 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 material with carbon element and/or material, preferably 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 existing
Any diaphragm material used in lithium ion battery, such as polyethylene, polypropylene, Kynoar and their MULTILAYER COMPOSITE
Film, but it is not limited only to these.
Hereinafter present context is described further, in the range of purport, implements various deformation be still included in this
In the claim of application, embodiment is only the mode that relatively sharp explanation is implemented, but the concrete side being not limited in embodiment
Formula.
Preparation example
The synthesis of [reference example 1] compound A
The first step is reacted:
Second step reacts:
Three-step reaction:
Operating procedure: addition 200ml dichloromethane is as solvent in the flask airtight with stirring, is subsequently adding first sulphur
Acyl chlorides (19.4g, 169.4mmol) is dissolved in 18.3g triethylamine slowly adding as reaction substrate, 15g bromoethanol (121mmol)
Enter in above-mentioned solution.After charging, continuing stirring reaction 3 hours, reaction terminates.Saturated aqueous common salt cleans reactant, point
From upper organic phase, heating removes solvent, obtains head product, and (eluting solvent is cyclohexane/ethyl acetate=3/ in silicagel column separation
2) purified product, obtains colorless oil 22.6g, the product compound1L-1-1 reacted as next step.
Above-claimed cpd 13g (64.0mmol) is dissolved in 25ml acetone and puts in the reaction bulb with stirring, then take
5.7g1-methylpyrrole (67.2mmol) joins above-mentioned solution, stirred under nitrogen atmosphere 2 days.After reaction terminates, to reactor
Middle addition 25ml ether, then reduce pressure suction filtration.Ether cleans solid product repeatedly, is dried to obtain compound1L-1-2
16.5g。
Product 16.5g (57.3mmol) obtained in the previous step is dissolved in 120ml methyl alcohol, weighs 11.1g KPF6Join
Stating in reaction substrate, under nitrogen protection, reaction stirring terminated after 2 days.Product is filtered, by appropriate methyl alcohol and second
Ether cleans solid product.Above-mentioned solid phase product is dissolved by the methanol/dichloromethane solution then preparing 8:7 (V/V), decompression
Filtering, collect filtrate, concentrate and obtain product 13.6g, this product is target compound A (compound1L-1).
The Structural Identification data of compound A:
1H NMR (400MHz, CD3OD-d4): δ 4.74 (bs, 2H), 3.88-3.85 (m, 2H), 3.71-3.61 (m, 4H),
3.23(s,3H),3.18(s,3H),2.28(m,4H).
LCMS(ESI)m/z 208.2(M-145)+.
The nuclear-magnetism of compound A identifies collection of illustrative plates as shown in Figure 1.
The synthesis of [reference example 2] compound B
The first step is reacted:
Second step reacts:
Three-step reaction:
Operating procedure: addition 200ml dichloromethane is as solvent in the flask airtight with stirring, is subsequently adding first sulphur
Acyl chlorides (19.4g, 169.4mmol) is dissolved in 18.3g triethylamine slowly adding as reaction substrate, 15g (121mmol) bromoethanol
Enter in above-mentioned solution.After charging, continuing stirring reaction 3 hours, reaction terminates.Saturated aqueous common salt cleans reactant, point
From upper organic phase, heating removes solvent, obtains head product, and (eluting solvent is cyclohexane/ethyl acetate=3/ in silicagel column separation
2) purified product, obtains colorless oil 22.6g, the product compound1L-1-1 reacted as next step.
Above-claimed cpd 22g (108.4mmol) is dissolved in 60ml acetone and puts in the reaction bulb with stirring, then take
11.3g 1-methyl piperidine (113.8mmol) joins above-mentioned solution, stirred under nitrogen atmosphere 3 days.After reaction terminates, to reaction
Adding 25ml ether in device, then reduce pressure suction filtration.Ether cleans solid product repeatedly, is dried to obtain compound1L-2-2
26g。
Product 26g (86.1mmol) obtained in the previous step is dissolved in 280ml methyl alcohol, weighs 16.6g KPF6(90.4mmol)
Joining in above-mentioned reaction substrate, under nitrogen protection, reaction stirring terminated after 3 days.Product is filtered, with appropriate
Methyl alcohol and ether clean solid product.Then the ethanol/methylene 1.8L solution of 8:7 (V/V) is prepared by above-mentioned solid phase product
Dissolving, filtration under diminished pressure, collect filtrate, concentrate and obtain product 20.5g, this product is target compound B
(compound1L-2)。
The Structural Identification data of compound B:
1H NMR(400MHz,CD3OD-d4):δ4.74(m,2H),3.86(m,2H),3.52-3.48(m,4H),3.22
(s,3H),3.20(s,3H),1.98-1.94(m,4H),1.77-1.69(m,2H).
LCMS(ESI)m/z 208.2(M-145)+。
The nuclear-magnetism of compound B identifies collection of illustrative plates as shown in Figure 2.
From the point of view of meeting the building-up process of compound of formula requirement above, it is only necessary to by piperidines and pyrroles and halogenosulfonic acid
Ester reaction can obtain has compound shown in the various formula I having and modifying functional group.
Such as, as R in formula I12During for unsaturated alkane, needing synthesizing halogen unsaturation alkane sulfonic acid ester, synthetic method is joined
Examine document: Stork G, Baine N H.Vinyl radical cyclization in the synthesis of
natural products:seychellene[J].Tetrahedron Letters,1985,26(48):5927-5930.
R12It is referred to document for synthetic method during alkyl ester group:
(1)Pospisil J.Towards antifungal compounds:total synthesis of
jerangolid D[D].UCL.,2006.
(2)Cheung C W,Ren P,Hu X.Mild and phosphine-free iron-catalyzed
cross-coupling of nonactivated secondary alkyl halides with alkynyl grignard
reagents[J].Organic letters,2014,16(9):2566-2569.
(3) Japan Patent Preparation of optically active 1,3-disubstituted
Azetidinones Jpn.Kokai Tokkyo Koho, 03246274,01, Nov 1991.
R12For referring to Japan Patent with alkyl cyano group side chain:
Preparation of 4-halo-3-hydroxybutanenitrile sulfonate ester,
Jpn.Kokai Tokkyo Koho,03153660,01,Jul 1991.
R13For alkyl except reference example 1, outside 2, reference may also be made to document: Coulomb J, Certal V, Larraufie M H,
et al.Intramolecular homolytic substitution of sulfinates and sulfinamides
[J].Chemistry–A European Journal,2009,15(39):10225-10232.
R13Document is referred to: Quinn R K for synthetic method during phenyl derivatives,Z A,Michalak S E,
et al.Site-Selective Aliphatic C–H Chlorination Using N-Chloroamides Enables
a Synthesis of Chlorolissoclimide[J].Journal of the American Chemical
Society,2015.
The change of anionicsite can be by reacting with corresponding alkali metal salt.
Embodiment
In following embodiment, comparative example and test example, reagent, material and the instrument used is as the most special
Explanation, be conventional reagent, conventional material and conventional instrument, the most commercially available, wherein involved reagent also can lead to
Cross conventional synthesis process synthesis to obtain.
In following embodiment, comparative example and test example, used reagent is as follows:
Additive:
Sulphonic acid ester cyclic quaternary ammonium salts: the compound 1 that is previously mentioned, compound 2, compound 3, compound 4.
Sultone compounds: the sultones 12 (1,3-propene sultone is called for short PST) mentioned in aforementioned table 1.
Electrolyte: lithium hexafluoro phosphate (LiPF6)。
Organic solvent: ethylene carbonate (EC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), propyl propionate (PP).
Positive electrode active materials: LiCoO2。
Barrier film: using PE porous polymer film as barrier film.
The preparation of embodiment 1 lithium ion battery (following be all called for short battery) 1～34
Battery 1～34 is prepared the most by the following method:
(1) prepared by negative plate
Negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber, thickener sodium carboxymethylcellulose are pressed
It is graphite according to weight ratio: acetylene black: butadiene-styrene rubber: sodium carboxymethylcellulose=95:2:2:1 mixes, adds deionized water
After, it is thoroughly mixed, forms uniform cathode size；This slurry is coated on negative current collector Copper Foil, then dry, cold
Pressure, obtains negative plate.
(2) prepared by positive plate
By positive electrode active materials cobalt acid lithium, conductive agent acetylene black, binding agent polyvinylidene fluoride by weight for cobalt acid lithium:
Acetylene black: polyvinylidene fluoride=96:2:2 mixes, adds solvent N-methyl pyrilidone, after being thoroughly mixed, shape
Uniformly 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 1～34 is prepared the most by the following method:
Water content < in the argon gas atmosphere glove box of 10ppm, be EC:EMC by EC, EMC, DEC, PP according to weight ratio:
After DEC:PP=3:3:2:2 mixes, obtain mixed solvent, then the electrolyte LiPF that will be fully dried6It is dissolved in above-mentioned mixed
In bonding solvent, then it is added thereto to sulphonic acid ester cyclic quaternary ammonium salts and sultone compounds, after stirring, it is thus achieved that electrolysis
Liquid, wherein LiPF6Concentration be 1mol/L.
(4) preparation of battery
Battery 1～34 prepares the most by the following method:
Positive plate, barrier film, negative plate are folded in order, makes barrier film be between positive/negative plate to play the work of isolation
With, then winding obtains naked battery core；Naked battery core is placed in external packing paper tinsel, the above-mentioned electrolyte prepared is injected into after drying
Battery in, be then passed through Vacuum Package, stand, be melted into, the operation such as shaping, it is thus achieved that battery.
Above-mentioned prepare battery during, used in electrolyte selected in each battery, each electrolyte
The kind of sulphonic acid ester cyclic quaternary ammonium salts and content thereof and the kind of sultone compounds and content thereof, as shown in table 2 below.
In table 2 below, the content of sulphonic acid ester cyclic quaternary ammonium salts and the content of sultone compounds are based on electricity
Solve the calculated percetage by weight of gross weight of liquid.
Table 2:
Comparative example lithium ion battery (following be all called for short battery) 1#～21#Preparation
Comparative example battery 1#～21#It is prepared the most by the following method:
Repeat the preparation of battery 1 in embodiment 1, wherein in the preparation of electrolyte, change sulphonic acid ester cyclic quaternary ammonium salts
Kind, content, and/or change the kind of sultone compounds, content, remaining condition is the most constant.
Above-mentioned prepare battery during, used in electrolyte selected in each battery, each electrolyte
The kind of sulphonic acid ester cyclic quaternary ammonium salts and content thereof and the kind of sultone compounds and content thereof, as shown in Table 3 below.
In Table 3 below, the content of sulphonic acid ester cyclic quaternary ammonium salts and the content of sultone compounds are based on electricity
Solve the calculated percetage by weight of gross weight of liquid.
Table 3
Note: in table 3, " " expression is not added with any kind of material.
Test case
(1) the high-temperature storage performance test of battery
The high-temperature storage performance of battery is characterized with the volume change before and after battery storage.
The battery prepared in embodiment and comparative example all carries out following test:
At 25 DEG C, first with the constant current of 0.5C, battery is charged to 4.6V, further with 4.6V constant-potential charge
It is 0.025C to electric current, then with drainage, battery is recorded in deionized water the initial volume of battery, by battery now
Initial volume as the volume before battery storage, then battery is placed at 85 DEG C storage 6h, after end to be stored, test electricity
Pond volume after storage at high temperatures, then calculates the volume change of battery by following formula.It addition, test result such as following table
Shown in 4.
The volume change (%) of battery=[volume before volume/battery storage after battery high-temperature storage] × 100%
(2) 45 DEG C of cycle performance tests 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, lithium rechargeable battery is charged to 4.6V, constant with 4.6V further
It is 0.025C that voltage charges to electric current, then with the constant current of 1C by battery discharge to 3.0V, this is a charge and discharge cycles
Process, this discharge capacity is the discharge capacity of the 1st circulation.Battery carries out repeatedly cycle charge discharge electrical measurement in a manner described
Examination, detection is obtained 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 4 below.
Capability retention (%) after 100 circulations of battery=[putting of the discharge capacity/1st time circulation of the 100th circulation
Capacitance] × 100%
Table 4
Related data from above-mentioned table 4, analyzes as follows:
(1) test result analysis of high-temperature storage performance
The volume change obtained by battery 1～34 and battery 1#In the contrast of the volume change obtained it can be seen that
Add sulphonic acid ester cyclic quaternary ammonium salts and sultone compounds in the electrolytic solution, it is possible to make battery have relatively low Volume Changes
Rate.
Due at battery 4#, battery 5#With battery 7#In, sulphonic acid ester cyclic quaternary ammonium salts and/or the weight of sultone compounds
Very little, the passivating film formed can not have the feature of compactness and stability concurrently to amount percentage composition, also cannot effectively stop work
Side reaction between property material and electrolyte, makes the volume change after battery storage too high.
In battery 1～7, the content of sultone compounds is 2%, adds the sulphonic acid ester that content is 0.1%～10%
Cyclic quaternary ammonium salts, can form composite passivation film densification, stable, stop the side reaction between active material and electrolyte, make
Battery has relatively low volume change after storage at high temperatures, and along with the increase of sulphonic acid ester cyclic quaternary salt content, battery exists
After storing 6h at 85 DEG C, Volume Changes raises after taking the lead in reducing.
In battery 3 and battery 8～13, the content of sulphonic acid ester cyclic quaternary ammonium salts is 2%, add content be 0.1%～
The sultone compounds of 10%, can form composite passivation film densification, stable, stop between active material and electrolyte
Side reaction, makes battery have relatively low volume change, and the increase of the content with sultone compounds after storage at high temperatures,
After battery stores 6h at 85 DEG C, there is relatively low volume change.Same, to battery 14～34 gained volume change
It is analyzed, there is analysis result same as described above.
(2) test result analysis of cycle performance
Capability retention after the circulation obtained by battery 1～34 and battery 1#Capability retention after the circulation obtained can
To find out, containing sulphonic acid ester cyclic quaternary ammonium salts and sultone compounds in electrolyte, battery has higher capability retention,
Battery has the cycle performance of excellence at 45 DEG C.
By battery 1#～21#Capability retention after the circulation obtained is it is known that electrolyte 1#In do not add any adding
Add agent so that organic solvent can produce more side reaction in pole piece, and the capability retention causing battery is low.
At battery 2#With battery 3#In, in respective electrolyte, add sulphonic acid ester cyclic quaternary ammonium salts, sultones respectively
Compound, owing to the passivating film formed can't stop the side reaction between active material and electrolyte effectively, so that electric
The cycle performance in pond substantially can not get improve.
Due at battery 4#, battery 5#With battery 7#In, sulphonic acid ester cyclic quaternary ammonium salts and/or the weight of sultone compounds
Very little, the composite passivation film formed can not have the feature of compactness and stability concurrently to amount percentage composition, it is impossible to effectively stops
Side reaction between active material and electrolyte, makes battery cycle performance at high temperature can not get effectively improving.
At battery 6#, battery 8#, battery 9#In, sulphonic acid ester cyclic quaternary ammonium salts or sultone compounds content are too much, too much
Sulphonic acid ester cyclic quaternary ammonium salts and sultone compounds remain in the electrolytic solution, continue pole piece react, cause interface
Impedance becomes big, deteriorates battery cycle performance at high temperature.
In battery 1～7, the content of sultone compounds is 2%, adds the sulphonic acid ester that content is 0.1%～10%
Cyclic quaternary ammonium salts, can form composite passivation film densification, stable, stop the side reaction between active material and electrolyte, make
Battery has higher capability retention after at high temperature circulating.
In battery 3 and battery 8～13, the content of sulphonic acid ester cyclic quaternary ammonium salts is 2%, add content be 0.1%～
The sultone compounds of 10%, can form composite passivation film densification, stable, stop between active material and electrolyte
Side reaction, makes battery have higher capability retention after at high temperature circulating.Same, to the appearance after battery 14～34 circulation
Amount conservation rate is analyzed, and has analysis result same as described above.
It can be seen that work as sulphonic acid ester cyclic quaternary ammonium salts and sultone compounds while of in electrolyte in from the above
Time, improving the capability retention after battery circulates at 45 DEG C, battery at high temperature has the cycle performance of excellence.
In sum: in the electrolytic solution, when the content of sulphonic acid ester cyclic quaternary ammonium salts is too small or excessive, when sultones
Compound content is too small or excessive, all can not form fine and close, stable, the preferable composite passivation film of interface performance, it is impossible to obtain
The at high temperature battery of good cycle.When electrolyte contain 0.1%～10% sulphonic acid ester cyclic quaternary ammonium salts and 0.1%～
The sultone compounds of 10%, especially contains sulphonic acid ester cyclic quaternary ammonium salts and the sultones of 1%～6% of 1%～6%
Compound, battery cycle performance at high temperature and high-temperature storage performance are the most excellent.
Embodiment 2
Preparing electrolyte by the method in embodiment 1, difference is, the formula of electrolyte is as shown in table 5, wherein in sulfonic acid
The structural formula of ester compounds is as shown in table 1:
Table 5
Lithium ion battery prepared by the electrolyte using embodiment 33～49 to prepare, its performance and above example phase
Seemingly, repeat no more as space is limited.
The announcement of book according to the above description, above-mentioned embodiment can also be carried out by the application those skilled in the art
Suitable change and amendment.Therefore, the application is not limited to detailed description of the invention disclosed and described above, to the application's
Some modifications and changes should also be as falling in the protection domain of claims hereof.
Claims (10)
1. an electrolyte, described electrolyte includes electrolyte, solvent and additive, it is characterised in that described additive includes
Sulphonic acid ester cyclic quaternary ammonium salts and sultone compounds.
Electrolyte the most according to claim 1, it is characterised in that the structural formula of described sulphonic acid ester cyclic quaternary ammonium salts such as formula I
Shown in:
In formula I, R11Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, replacement or unsubstituted
C2～12Alkynyl, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted C1～12Acyloxy；
R12Selected from substituted or unsubstituted C1～12Alkylidene, substituted or unsubstituted C2～12Alkenylene, substituted or unsubstituted
C2～12Alkynylene, substituted or unsubstituted C1～12Alkylene acyl group；
R13Selected from substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C2～12Thiazolinyl, substituted or unsubstituted C2～12Alkynes
Base, substituted or unsubstituted C1～12Alkoxyl, substituted or unsubstituted C1～12Acyloxy, substituted or unsubstituted C6～22Aryl,
Substituted or unsubstituted C5～22Heterocyclic base；
R14Selected from substituted or unsubstituted C1～3Alkylidene；
Substituent is selected from cyano group, halogen；
X-Represent anion.
Electrolyte the most according to claim 2, it is characterised in that R11、R13The most independent is respectively selected from replacement or does not takes
The C in generation1～6Alkyl, R12Selected from substituted or unsubstituted C1～12Alkylidene, R14Selected from substituted or unsubstituted C1～2Alkylidene.
Electrolyte the most according to claim 2, it is characterised in that the cation group choosing of described sulphonic acid ester cyclic quaternary ammonium salts
From following structural formula:
Electrolyte the most according to claim 2, it is characterised in that the anion X of described sulphonic acid ester cyclic quaternary ammonium salts—It is selected from
Following group:
F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、(FSO2)2N-、
Electrolyte the most according to claim 1, it is characterised in that described sultone compounds is selected from such as Formula II A, formula
At least one in IIB, Formula II C or Formula II D compound；
Wherein, R21、R22、R23、R24It is respectively selected from hydrogen atom, halogen, nitro, cyano group, carboxyl, sulfonic group, replacement independently of one another
Or unsubstituted C1～20Alkyl, substituted or unsubstituted C2～20Thiazolinyl, substituted or unsubstituted C2～20Alkynyl, replacement or unsubstituted
C1～20Alkoxyl, substituted or unsubstituted C1～20Alkanoyl, substituted or unsubstituted C1～20Alkane ether；Substituent is selected from halogen
Element, nitro, cyano group, carboxyl or sulfonic group.
Electrolyte the most according to claim 6, it is characterised in that described sultone compounds is selected from such as Formula II A ', formula
At least one in IIB ', Formula II C ' or Formula II D ' compound；
Wherein, R21’、R22’、R23’、R24' it is respectively selected from substituted or unsubstituted C independently of one another1～6Straight or branched alkyl, take
Generation or unsubstituted C5～7Cycloalkyl, substituted or unsubstituted C2～6Thiazolinyl, substituted or unsubstituted C2～6Alkynyl, substituent is selected from
Halogen or cyano group.
Electrolyte the most according to claim 1, it is characterised in that described sulphonic acid ester cyclic quaternary ammonium salts matter in the electrolytic solution
Amount percentage is 0.1%～10%, preferably 1%～6%；Described sultone compounds mass percent in the electrolytic solution
It is 0.1%～10%, preferably 1%～6%.
Electrolyte the most according to claim 1, it is characterised in that described electrolyte includes lithium hexafluoro phosphate, tetrafluoro boric acid
Lithium, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate, LiN (SO2Rf)2、LiN(SO2F)(SO2Rf), double fluoroform sulphur
At least one in imide li, double (fluorine sulphonyl) imine lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, wherein, Rf=
CnF2n+1, n is the integer of 1～10, preferably lithium hexafluoro phosphate or LiN (SO2Rf)2。
10. a lithium ion battery, it is characterised in that include the positive plate containing positive electrode active materials, containing negative electrode active material
The electrolyte according to any one of negative plate, barrier film and claim 1～9 expected.
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