CN105958120A - Electrolyte and lithium ion battery using same - Google Patents
Electrolyte and lithium ion battery using same Download PDFInfo
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- CN105958120A CN105958120A CN201610490124.1A CN201610490124A CN105958120A CN 105958120 A CN105958120 A CN 105958120A CN 201610490124 A CN201610490124 A CN 201610490124A CN 105958120 A CN105958120 A CN 105958120A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
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Abstract
The application belongs to the lithium ion battery field, specifically says, this application relates to an electrolyte and uses lithium ion battery of this electrolyte. The electrolyte comprises an organic solvent, an electrolyte and an additive, wherein the additive comprises an additive A and an additive B; the additive A is selected from at least one of sulfoxide compounds, sulfone compounds, sulfite compounds, sulfate compounds and methylene methanedisulfonate; the additive B is selected from at least one of lithium difluorophosphate or a compound shown as a formula I; the electrolyte can reduce the direct current impedance of a fresh lithium ion battery and the direct current impedance of a battery after circulation.
Description
Technical field
The application belongs to field of lithium ion battery, and specifically, the application relates to a kind of electrolyte and use
The lithium ion battery of this electrolyte.
Background technology
Lithium ion battery is because having the advantages such as specific energy is high, have extended cycle life, self discharge is little, by extensively
It is applied in consumer electronics product and energy storage and electrokinetic cell.Along with extensively should of lithium ion battery
With, it uses environment to tend to varied the most already, and the requirement to battery is more and more higher.Battery makes
Often a large amount of heat production because charging current or discharge current are excessive during with, to equipment and human body
Cause certain injury.
Battery in the caloric value of unit interval in addition to by Guan Bi, circuital current size affected, also can be with
The DC internal resistance of battery is relevant, and the biggest caloric value of DC internal resistance is the biggest, and antisense is the least.Cathode impedance
In battery DC internal resistance, account for the biggest proportion, for electrolyte, reduce the DC impedance of battery
Can set about with electrolyte solid electrolyte interface (SEI) impedance from reducing negative pole, relatively low negative pole
Interface impedance not only can reduce the DC impedance of battery, reduces the heat production of battery, it is also possible to reduces negative
The risk of pole analysis lithium.
In view of this, special proposition the application.
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 using 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, including organic solvent, electrolyte and additive, described interpolation
Agent includes additive A and additive B；Described additive A is selected from sulfoxide compound, sulfone class
In compound, sulfite compounds, sulfuric acid ester compound, methane-disulfonic acid methylene ester at least
A kind of；Described additive B is selected from least in difluorophosphate or the compound as shown in formula I
Kind；
In formula I, R11、R12、R13It is respectively selected from substituted or unsubstituted C independently of one another1～20
Alkyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C1～20Alkoxyl, replacement or
Unsubstituted C6～26Aryloxy group,Wherein, R ', R ", R " '
The most independent is respectively selected from substituted or unsubstituted C1～20Alkyl；Or R11、R12、R13In two
Individual substituent group connects formation 3～10 rings, possibly together with oxygen atom or silicon atom in described 3～10 rings
In at least one；
Substituent group is selected from halogen, cyano group, C1～4Alkyl.
Preferably, at least one in the compound as shown in formula I A of described additive B；
In formula I A, expression C, O or Si respectively that X, Y are the most independent；R14Selected from replace or
Unsubstituted C1～10Alkylidene, substituent group is selected from halogen, cyano group；
Preferably, at least one in the compound as shown in formula I Aa of described additive B；
In formula I Aa, R13' selected from substituted or unsubstituted C1～10Alkyl, substituted or unsubstituted
C1～10Alkoxyl, R14' selected from substituted or unsubstituted C2～4Alkylidene, substituent group is selected from halogen, cyanogen
Base.
Preferably, R11、R12、R13The most independent is respectively selected from substituted or unsubstituted C1～6Alkyl,
Substituted or unsubstituted C1～6Alkoxyl；Substituent group is selected from halogen, cyano group.
Preferably, described additive B is selected from trimethyl phosphate, triethyl phosphate, methyl acid phosphate diformazan
Ester, methyl acid phosphate diethylester or such as at least one in the compound of formula 1 structure:
Preferably, described sulfoxide compound in the compound as shown in formula II A at least one,
Described sulfone compound in the compound shown in formula II B at least one, as described in sulfurous esters
Compound in the compound shown in formula II C at least one, as described in sulfuric acid ester compound be selected from
At least one in compound as shown in formula II D；
Wherein, R21、R22It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement
Or unsubstituted C2～20Thiazolinyl；
R23、R24It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement or do not take
The C in generation2～20Thiazolinyl, or R23、R24Connect and form 4～10 rings；
R25、R26It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement or do not take
The C in generation2～20Thiazolinyl, or R25、R26Connect and form 5～10 rings；
R27、R28It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement or do not take
The C in generation2～20Thiazolinyl ,-Si (R ')3, or R27、R28Connect and form 5～10 rings；R ' for replace or
Unsubstituted C1～6Alkyl；
Substituent group is selected from halogen.
Preferably, at least during described sulfoxide compound is selected from dimethyl sulfoxide, diethyl sulfoxide
Kind；Described sulfone compound is preferably selected from least one in dimethyl sulfone, diethyl sulfone, sulfolane；
Described sulfite compounds is preferably selected from ethylene sulfite, propylene sulfite, 4-methyl Asia
At least one in sulfuric acid vinyl ester, dimethyl sulfite, sulfurous acid diethyl ester, sulfurous acid methyl ethyl ester；
Described sulfuric acid ester compound preferably sulfuric acid ethyl, 4-methyl ethyl sulfate, sulphuric acid Asia propyl ester,
At least one in trimethyl silane sulfuric ester.
Preferably, the content of described additive A is the 0.01%～3% of described electrolyte gross mass,
It is preferably 0.1%～1%.
Preferably, the content of described additive B is the 0.01%～3% of described electrolyte gross mass,
It is preferably 0.1%～1%.
Preferably, described organic solvent selected from ethylene carbonate, propylene carbonate, dimethyl carbonate,
Diethyl carbonate, dipropyl carbonate, Ethyl methyl carbonate, methyl formate, Ethyl formate, ethyl propionate,
Propyl propionate, methyl butyrate, ethyl acetate, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N-
At least one in methylacetamide, acetonitrile, methyl sulfide.
The application relates to a kind of lithium ion battery, and it includes electrolyte, positive plate, negative plate, isolation
Film and package foil；Described positive plate includes plus plate current-collecting body and the cathode film being coated on plus plate current-collecting body
Sheet, negative plate includes negative current collector and the cathode membrane being coated on negative current collector；Its feature exists
In, described electrolyte is the electrolyte of the application.
The technical scheme of the application at least has a following beneficial effect:
When generally the compound containing S=O key uses as solvent, viscosity is relatively big, can increase the direct current of battery
Internal resistance, and when using separately as cathode film formation additive, SEI impedance can raise, as dimethyl is sub-
Sulfone, dimethyl sulfone, after interpolation, SEI impedance substantially increases；Compound containing P=key also has higher
Viscosity, uses the DC impedance that can not reduce battery, separately as cathode film formation additive as solvent
During use, SEI impedance the most substantially reduces, and the SEI formed is more unstable, under high temperature easily
Decompose, the cycle performance of battery is affected bigger.The application studies discovery, by the application containing S=O
After the compound (additive A) of key and the compound (additive B) containing P=O key are applied in combination, can
Significantly to reduce SEI impedance, the growth of SEI impedance in suppression cyclic process.Its reason can consider
As follows (but being not limited to this): after cathode film formation additive A and B are applied in lithium ion battery,
The SEI phosphate particle formed containing P=O key compound reduction decomposition product is embedded in containing S=O key
In the formation SEI of compound, form composite solid electrolyte interface (SEI) film of densification in negative terminal surface,
Adding the ionic conductivity of SEI film, in suppression cyclic process, SEI impedance increases again.
Detailed description of the invention
Below in conjunction with specific embodiment, the application is expanded on further.Should be understood that these embodiments are only used
In explanation the application rather than restriction scope of the present application.
The application relates to a kind of electrolyte, it is possible to battery after the DC impedance of reduction fresh cells and circulation
DC impedance.This electrolyte includes organic solvent, electrolyte and additive, containing making in additive
Additive A and additive B for cathode film formation additive；
Wherein, additive A is the compound containing S=O key, selected from sulfoxide compound, sulfone class
In compound, sulfite compounds, sulfuric acid ester compound, methane-disulfonic acid methylene ester extremely
Few one；
Additive B is the compound containing P=O key, selected from difluorophosphate (LiPO2F2) and formula
At least one of the compound of I structure:
In formula I, R11、R12、R13It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkane
Base, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C1～20Alkoxyl, replacement or not
Substituted C6～26Aryloxy group,Wherein, R ', R ", R " '
The most independent is respectively selected from substituted or unsubstituted C1～20Alkyl；Or R11、R12、R13In two
Individual substituent group connects formation 3～10 rings, possibly together with oxygen atom or silicon atom in described 3～10 rings
In at least one；
Substituent group is selected from halogen, cyano group, C1～4Alkyl.
As a kind of improvement of the application electrolyte, when substituent group is straight chain or straight chain substituent, R11、
R12、R13It is respectively selected from substituted or unsubstituted C independently of one another1～6Alkoxyl, replacement or unsubstituted
Phenyl,Wherein, R ', R ", R " ' the most independent point
Xuan Zi substituted or unsubstituted C1～6Alkyl；
Substituent group is selected from halogen, C1～4Alkyl.
As a kind of improvement of the application electrolyte, when two substituent groups in substituent group connect cyclization
Time, be preferably formed as 4～10 rings, more preferably form 4～8 rings, most preferably formed five-membered ring or
Hexatomic ring.In this circulus, in addition to a P atom and carbon atom, also can containing oxygen atom or
Silicon atom, preferably comprises 1～2 oxygen atom.
As a kind of improvement of the application electrolyte, additive B is selected from the compound as shown in formula I A
In at least one；
In formula I A, expression C, O or Si respectively that X, Y are the most independent；
R14Selected from substituted or unsubstituted C1～10Alkylidene；Substituent group is selected from halogen, cyano group.
For a kind of improvement of the application electrolyte, in formula I A, the difference table that X, Y are the most independent
Show C or O, R14Selected from substituted or unsubstituted C2～6Alkylidene；Substituent group is selected from halogen, cyano group.
As a kind of improvement of the application electrolyte, additive B is selected from the chemical combination as shown in formula I Aa
At least one in thing；
In formula I Aa, R13' selected from substituted or unsubstituted C1～10Alkyl, substituted or unsubstituted
C1～10Alkoxyl, R14' selected from substituted or unsubstituted C2～4Alkylidene, substituent group is selected from halogen, cyanogen
Base.
As a kind of improvement of the application electrolyte, in formula I Aa, R13' selected from replacing or not taking
The C in generation1～6Alkyl, R14' selected from substituted or unsubstituted C2～4Alkylidene；Substituent group selected from halogen,
Cyano group.
As a kind of improvement of the application electrolyte, R11、R12、R13The most independent being respectively selected from takes
Generation or unsubstituted C1～6Alkyl, substituted or unsubstituted C1～6Alkoxyl；Substituent group selected from halogen,
Cyano group.
In the formula of the application:
Carbon number is the alkyl of 1～20, and alkyl can be chain-like alkyl, it is possible to for cycloalkyl, be positioned at
The ring hydrogen of cycloalkyl can be replaced by alkyl, and in described alkyl, the preferred lower limit of carbon number is 2,
3,4,5, preferred higher limit is 3,4,5,6,8,10,12,14,16,18.Preferably,
The alkyl selecting carbon number to be 1～12, 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
Being the chain-like alkyl of 1～4, carbon number is the cycloalkyl of 5～7.As the example of alkyl, specifically
Can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, uncle
Butyl, 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 is the aryl of 6～26, such as phenyl, benzene alkyl, at least contains a phenyl
Aryl such as xenyl, condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base also may be used
Replaced by alkyl or thiazolinyl.Preferably, the aryl selecting carbon number to be 6～16, further
Preferably, the aryl selecting carbon number to be 6～14, it is further preferred that select carbon number
It it is the aryl of 6～9.As the example of aryl, specifically can enumerate: phenyl, benzyl, xenyl,
P-methylphenyl, o-tolyl, a tolyl.
When in the alkyl that the aforementioned carbon number being previously mentioned is 1～20 containing oxygen atom, it can be alcoxyl
Base.Preferably, the alkoxyl selecting carbon number to be 1～10, it is further preferred that select carbon former
Subnumber is the alkoxyl of 1～6, it is further preferred that the alkoxyl selecting carbon number to be 1～4.
As the example of alkoxyl, specifically can enumerate: methoxyl group, ethyoxyl, positive propoxy, isopropyl oxygen
Base, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy,
Cyclohexyloxy.
When in the aryl that the aforementioned carbon number being previously mentioned is 6～26 containing oxygen atom, can be virtue oxygen
Base.Preferably, the aryloxy group selecting carbon number to be 6～16, it is further preferred that select carbon former
Subnumber is the aryloxy group of 6～14, it is further preferred that the aryloxy group selecting carbon atom to be 6～10.
As the example of aryloxy group, specifically can enumerate: phenoxy group, benzyloxy, 4-methylphenoxy, 3,5-
Dimethyl phenoxy, 4-methylbenzyloxy, 3-methylbenzyloxy, 2,6-diisopropyl benzyloxy, 1-
Naphthoxy.
Carbon number be the alkylidene of 1～10 be straight or branched alkylidene, in described alkylidene, carbon is former
The preferred lower limit of subnumber is 2,3,4,5, and preferred higher limit is 3,4,5,6,8,9.
Preferably, the alkylidene selecting carbon number to be 1～6.As the example of alkyl, specifically can lift
Go out: methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, sub-sec-butyl,
Pentylidene, hexylidene.
As a kind of improvement of the application electrolyte, when substituent group not cyclization in formula I, additive
At least one in following structural formula of B:
Wherein, when the substituent group in formula I is straight or branched substituent group, additive B is further selected from
At least one in following structural formula:
As a kind of improvement of the application electrolyte, when substituent group cyclization in formula I, additive B
At least one in following structural formula:
As a kind of improvement of the application electrolyte, sulfoxide compound is changed selected from as shown in formula II A
In compound at least one, sulfone compound in the compound as shown in formula II B at least one,
Sulfite compounds is selected from least one in compound as shown in formula II C, sulfuric acid ester chemical combination
At least one in compound as shown in formula II D of thing；
Wherein, R21、R22It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement
Or unsubstituted C2～20Thiazolinyl；
R23、R24It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement or do not take
The C in generation2～20Thiazolinyl, or R23、R24Connect and form 4～10 rings；
R25、R26It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement or do not take
The C in generation2～20Thiazolinyl, or R25、R26Connect and form 5～10 rings；
R27、R28It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement or do not take
The C in generation2～20Thiazolinyl ,-Si (R ')3, or R27、R28Connect and form 5～10 rings；R ' for replace or
Unsubstituted C1～6Alkyl；
Substituent group is selected from halogen.
Preferably, R21、R22It is respectively selected from substituted or unsubstituted C independently of one another1～6Alkyl, take
Generation or unsubstituted C2～6Thiazolinyl；R23、R24It is respectively selected from substituted or unsubstituted independently of one another
C1～6Alkyl, substituted or unsubstituted C2～6Thiazolinyl；R25、R26It is respectively selected from replacement independently of one another
Or unsubstituted C1～6Alkyl, substituted or unsubstituted C2～6Thiazolinyl；R27、R28Divide independently of one another
Xuan Zi substituted or unsubstituted C1～6Alkyl, substituted or unsubstituted C2～6Thiazolinyl ,-Si (R ')3；R’
For substituted or unsubstituted C1～6Alkyl.
Wherein, the ring that in each structural formula, substituent group connects into includes saturated rings and unsaturated ring.Preferably
, in formula II C, R25、R26Connect and form 5～10 saturated rings or double with a carbon carbon
5～10 rings of key；In formula II D, R27、R28Connect and form 5～10 saturated ring or bands
There are 5～10 rings of a carbon-carbon double bond.
As a kind of improvement of the application electrolyte,
At least one in following compound of sulfoxide compound:
At least one in following compound of sulfone compound:
At least one in following compound of sulfite compounds:
At least one in following compound of sulfuric acid ester compound:
As a kind of improvement of the application electrolyte, the content of additive A is electrolyte gross mass
0.01%～3%；Upper limit value is 1%, 2%, 2.5%, 2.75%, lower limit value is 0.05%,
0.1%, 0.5%.The content of additive A can be by any number structure in upper limit value and lower limit value
Become its content.This is because when the content of additive A is less than 0.01%, it is impossible to it is passivated negative pole completely
Surface, thus can not effectively stop the side reaction caused by the electron transfer between electrolyte and electrode,
Reduce SEI impedance；And when additive A content is more than 3%, can be formed thicker at positive electrode surface
Passivating film, causes lithium ion mobility resistance to increase, and increases the heating of battery.It is further preferred that institute
Stating positive pole passivation protection agent mass fraction in the electrolytic solution is 0.1%～1%.
As a kind of improvement of the application electrolyte, the content of additive B is electrolyte gross mass
0.01%～3%；Upper limit value is 1%, 2%, 2.5%, 2.75%, lower limit value is 0.05%,
0.1%, 0.5%.The content of additive B can be by any number structure in upper limit value and lower limit value
Become its content.This is because when the content of additive B is less than 0.01%, it is impossible to it is passivated negative pole completely
Surface, thus can not effectively stop the side reaction caused by the electron transfer between electrolyte and electrode,
Reduce SEI impedance；And when additive B content is more than 2%, can be formed thicker at positive electrode surface
Passivating film, causes lithium ion mobility resistance to increase, and increases the heating of battery.It is further preferred that institute
Stating positive pole passivation protection agent mass fraction in the electrolytic solution is 0.1%～1%.
As a kind of improvement of the application electrolyte, solvent selected from ethylene carbonate, propylene carbonate,
Dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Ethyl methyl carbonate, methyl formate, formic acid second
Ester, ethyl propionate, propyl propionate, methyl butyrate, ethyl acetate, N-Methyl pyrrolidone, N-
At least one in methylformamide, N-methylacetamide, acetonitrile, methyl sulfide.
As a kind of improvement of the application electrolyte, electrolyte is optionally from organic bath or inorganic electrolyte
At least one in matter.
As a kind of improvement of the application electrolyte, containing fluorine element, boron element, phosphorus unit in electrolyte
At least one in element.
As a kind of improvement of the application electrolyte, electrolyte is selected from lithium hexafluoro phosphate LiPF6、LiBF4、
LiBOB, double trifluoromethanesulfonimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), double (fluorine
Sulphonyl) imine lithium Li (N (SO2F)2) at least one in (being abbreviated as LiFSI).
In order to realize foregoing invention purpose, present invention also provides a kind of lithium ion battery, it includes electricity
Solve liquid, positive plate, negative plate, isolating membrane and package foil；Positive plate includes plus plate current-collecting body and coating
Positive pole diaphragm on plus plate current-collecting body, negative plate includes negative current collector and is coated on negative current collector
On cathode membrane；Electrolyte is the electrolyte of any of the above-described paragraph.
As a kind of improvement of the application lithium ion battery, positive pole diaphragm includes positive electrode active materials, glues
Knot agent and conductive agent.
As a kind of improvement of the application lithium ion battery, positive electrode active materials is optionally from cobalt acid lithium
LiCoO2, lithium-nickel-manganese-cobalt ternary material, phosphonic acids ferrous lithium, at least one in LiMn2O4, or cobalt
Acid lithium and the mixture of lithium-nickel-manganese-cobalt ternary material.
As a kind of improvement of the application lithium ion battery, cathode membrane includes negative active core-shell material, glues
Knot agent and conductive agent.
As a kind of improvement of the application lithium ion battery, negative active core-shell material is material with carbon element and/or siliceous
Material, preferably graphite and/or silicon.
In following embodiment, comparative example and test example, the reagent, material and the instrument that are used are such as
There is no specified otherwise, the most commercially obtain.
In the following embodiments, in comparative example and test example, used material is as follows:
Solvent: ethylene carbonate (EC), diethyl carbonate (being abbreviated as DEC).
Electrolyte: LiPF6。
Compound:
Additive A: dimethyl sulfoxide (DMSO), dimethyl sulfone (MSM), sulfolane (SL),
Ethylene sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS), 4-
Methyl ethyl sulfate (PPS), sulphuric acid Asia propyl ester (PCS)；
Additive B: difluorophosphate (LiPO2F2), trimethyl phosphate (TMP), shown in formula 1
Compound；
Lithium battery diaphragm: (model is A273 to 16 microns of thick polypropylene isolating membrane, by Celgard
Company provides).
Embodiment 1
Electrolyte 1～16 is prepared by the following method:
In drying shed, after EC and DEC is mixed, add electrolyte, be subsequently adding cyclic lactone class
Compound and additive, mix homogeneously, it is thus achieved that electrolyte, wherein, the addition of EC and DEC is
Making EC and DEC weight ratio is EC:DEC=3:7, and the addition of electrolyte is for making LiPF6?
Molar concentration in electrolyte is 1mol/L.
The preparation method of lithium ion battery:
Positive plate, lithium battery isolation membrane, negative plate are folded in order, makes lithium battery isolation membrane be in
Playing the effect of isolation between positive and negative plate, then winding obtains naked battery core；Outside naked battery core is placed in
In package foil, the above-mentioned electrolyte prepared is injected in dried battery, through Vacuum Package,
The operations such as standing, chemical conversion, shaping, it is thus achieved that battery.
During above-mentioned preparation, the concrete kind of used additive and consumption thereof such as table 1 below
Shown in.The content of additive is the calculated percetage by weight of gross weight based on electrolyte.
Comparative example electrolyte 1#～13# is prepared according to the method for embodiment, differs only in, electrolyte
Composition and the addition of middle additive are as shown in table 1.
Electrolysis additive compound mode in table 1, embodiment and comparative example and addition
Note: in table 1 above, " " represents without this corresponding in the table material.
The lithium ion battery above-mentioned comparative example and embodiment prepared, carries out following performance test.
Test one, loop test
The lithium ion battery prepared is carried out respectively following test:
At 25 DEG C, by lithium ion battery, with 0.5C constant-current charge to 4.35V, then constant voltage is filled
Electricity to electric current is 0.05C, then with 0.5C constant-current discharge to 3.0V, now for circulate first, according to
Above-mentioned condition carries out time so repeatedly cycle charging/electric discharge, calculates lithium ion battery circulation 300
Capability retention after secondary, often organizes each 5 batteries, wherein, the capability retention after circulation according under
Formula calculates.Electrolyte selected in each lithium ion battery and the relevant test data obtained
See table 2.
Capability retention after circulation=(discharge capacity after circulation/circulate first discharge capacity)
× 100%, the result of loop test is as shown in table 2.
Test two, DC internal resistance (DCR) test
With 0.5C constant-current charge to 4.35V at 25 DEG C, constant-voltage charge to electric current is 0.05C, stops
Sleep 1 hour, then with 0.5C 60 minutes (50%SOC) of electric discharge, dormancy 1 hour；Then with 0.1C
Discharge 10 seconds, voltage V during record end1, then discharge 1 second with 1C, voltage V during record end2,
Calculate battery DCR, DCR computing formula: DCR=(V1-V2)/(I1C-I0.1C), unit is mOhm.
The DCR of battery after test fresh cells and 300 circulations, and calculate DCR rate of increase, DCR increases
Rate computing formula is:
Battery after DCR rate of increase=(battery DCR before battery DCR-circulation after circulation)/circulation
DCR × 100%
Electrolyte selected in each lithium ion battery and the relevant test data obtained see table
2。
The dependence test result of table 2, each comparative example and embodiment battery
Thus it is known that the electrolyte that the application is provided, after being applied in lithium ion battery, drop
The DCR of low fresh cells, after further can reducing circulation, battery DCR increases.It addition, work as
Electrolyte includes additive A that the present invention provides simultaneously and during additive B, additive A and
Additive B forms stable SEI in negative terminal surface jointly, it is possible to increase the cycle performance of battery.
Thus it is known that the application provide electrolyte, after being applied in lithium ion battery, it is possible to
In the DCR of reduction lithium ion battery and cyclic process, DCR increases, and does not affect the cyclicity of battery
Energy.
Embodiment 2
The present embodiment electrolyte is prepared according to the method for embodiment 1, differs only in, and adds in electrolyte
The composition and the addition that add agent are as shown in table 3.
Table 3:
The electrolyte of the present embodiment is prepared lithium ion battery according to the method for embodiment 1, and according to reality
The performance of battery is detected by the method executed in example 1, detection obtain the performance of battery 17～33 with
Above example is similar, repeats no more as space is limited.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be right
Above-mentioned embodiment carries out suitable change and amendment.Therefore, the invention is not limited in and be disclosed above
Some modifications and changes of the present invention be should also be as falling into the present invention's by the detailed description of the invention with describing
In scope of the claims.Although additionally, this specification employs some specific terms,
But these terms are merely for convenience of description, the present invention is not constituted any restriction.
Claims (10)
1. an electrolyte, including organic solvent, electrolyte and additive, it is characterised in that: described
Additive includes additive A and additive B；Described additive A is selected from sulfoxide compound, sulfone
In compounds, sulfite compounds, sulfuric acid ester compound, methane-disulfonic acid methylene ester
At least one；Described additive B is selected from difluorophosphate or the compound as shown in formula I at least
A kind of；
In formula I, R11、R12、R13It is respectively selected from substituted or unsubstituted C independently of one another1～20
Alkyl, substituted or unsubstituted C6～26Aryl, substituted or unsubstituted C1～20Alkoxyl, replacement or
Unsubstituted C6～26Aryloxy group,Wherein, R ', R ", R " '
The most independent is respectively selected from substituted or unsubstituted C1～20Alkyl；Or R11、R12、R13In two
Individual substituent group connects formation 3～10 rings, possibly together with oxygen atom or silicon atom in described 3～10 rings
In at least one；
Substituent group is selected from halogen, cyano group, C1～4Alkyl.
Electrolyte the most according to claim 1, it is characterised in that described additive B is selected from such as
At least one in compound shown in formula I A；
In formula I A, expression C, O or Si respectively that X, Y are the most independent；R14Selected from replace or
Unsubstituted C1～10Alkylidene, substituent group is selected from halogen, cyano group；
Preferably, at least one in the compound as shown in formula I Aa of described additive B；
In formula I Aa, R13' selected from substituted or unsubstituted C1～10Alkyl, substituted or unsubstituted
C1～10Alkoxyl, R14' selected from substituted or unsubstituted C2～4Alkylidene, substituent group is selected from halogen, cyanogen
Base.
Electrolyte the most according to claim 1, it is characterised in that R11、R12、R13The most solely
Vertical is respectively selected from substituted or unsubstituted C1～6Alkyl, substituted or unsubstituted C1～6Alkoxyl；
Substituent group is selected from halogen, cyano group.
Electrolyte the most according to claim 1, it is characterised in that described additive B is selected from phosphorus
Acid trimethyl, triethyl phosphate, methyl-phosphoric acid dimethyl ester, methyl acid phosphate diethylester or such as formula 1 structure
Compound at least one:
Electrolyte the most according to claim 1, it is characterised in that described sulfoxide compound selects
At least one in compound shown in formula II A, described sulfone compound are selected from as shown in formula II B freely
At least one in compound, described sulfite compounds are in compound as shown in formula II C
At least one, at least one in the compound as shown in formula II D of described sulfuric acid ester compound；
Wherein, R21、R22It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement
Or unsubstituted C2～20Thiazolinyl；
R23、R24It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement or do not take
The C in generation2～20Thiazolinyl, or R23、R24Connect and form 4～10 rings；
R25、R26It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement or do not take
The C in generation2～20Thiazolinyl, or R25、R26Connect and form 5～10 rings；
R27、R28It is respectively selected from substituted or unsubstituted C independently of one another1～20Alkyl, replacement or do not take
The C in generation2～20Thiazolinyl ,-Si (R ')3, or R27、R28Connect and form 5～10 rings；R ' for replace or
Unsubstituted C1～6Alkyl；
Substituent group is selected from halogen.
Electrolyte the most according to claim 1, it is characterised in that described sulfoxide compound selects
At least one in dimethyl sulfoxide, diethyl sulfoxide；Described sulfone compound is preferably selected from diformazan
At least one in base sulfone, diethyl sulfone, sulfolane；Described sulfite compounds is preferably selected from
Ethylene sulfite, propylene sulfite, 4-methyl ethylene sulfite, dimethyl sulfite, Asia
At least one in dithyl sulfate, sulfurous acid methyl ethyl ester；Described sulfuric acid ester compound preferably sulfuric acid
In ethyl, 4-methyl ethyl sulfate, sulphuric acid Asia propyl ester, trimethyl silane sulfuric ester at least one
Kind.
Electrolyte the most according to claim 1, it is characterised in that the content of described additive A
For the 0.01%～3% of described electrolyte gross mass, preferably 0.1%～1%.
Electrolyte the most according to claim 1, it is characterised in that the content of described additive B
For the 0.01%～3% of described electrolyte gross mass, preferably 0.1%～1%.
Electrolyte the most according to claim 1, it is characterised in that described organic solvent is selected from carbon
Acid ethyl, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbonic acid first
Ethyl ester, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, methyl butyrate, ethyl acetate,
In N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, methyl sulfide at least
A kind of.
10. a lithium ion battery, it includes electrolyte, positive plate, negative plate, isolating membrane and bag
Dress paper tinsel；Described positive plate includes plus plate current-collecting body and the positive pole diaphragm being coated on plus plate current-collecting body, negative
Pole piece includes negative current collector and the cathode membrane being coated on negative current collector；It is characterized in that, institute
Stating electrolyte is the electrolyte according to any one of claim 1 to 9.
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