CN105958120B - Electrolyte and lithium ion battery using same - Google Patents
Electrolyte and lithium ion battery using same Download PDFInfo
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- CN105958120B CN105958120B CN201610490124.1A CN201610490124A CN105958120B CN 105958120 B CN105958120 B CN 105958120B CN 201610490124 A CN201610490124 A CN 201610490124A CN 105958120 B CN105958120 B CN 105958120B
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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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application 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 sulfoxide compound, sulfone compound, sulfite compound, and methaneAt least one of methylene disulfonate; 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, specifically, this application involves a kind of electrolyte and uses the electrolyte
Lithium ion battery.
Background technique
Lithium ion battery is because having many advantages, such as that specific energy is high, having extended cycle life, self discharge is small, is widely used in consumer
In electronic product and energy storage and power battery.With the extensive use of lithium ion battery, use environment also tends to be more already
Kind multiplicity, the requirement to battery are higher and higher.Battery is during use often because charging current or discharge current are excessive
And a large amount of heat production, equipment and human body are caused centainly to injure.
Battery the unit time calorific value other than being influenced by closed circuit size of current, can also be with the direct current of battery
Internal resistance is related, and DC internal resistance is bigger, and calorific value is bigger, and antisense is then smaller.Cathode impedance accounts for very big in battery DC internal resistance
Specific gravity, for electrolyte, the DC impedance for reducing battery can be from reduction cathode and electrolyte solid electrolyte interface (SEI)
Impedance is set about, and lower cathode interface impedance can not only reduce the DC impedance of battery, reduce the heat production of battery, can also drop
The risk of low cathode analysis lithium.
In view of this, special propose the application.
Summary of the invention
The primary goal of the invention of the application is to propose a kind of electrolyte.
The second goal of the invention of the application is to propose a kind of lithium ion battery using the electrolyte.
In order to complete the purpose of the application, the technical solution of use are as follows:
This application involves a kind of electrolyte, including organic solvent, electrolyte and additive, the additive includes additive
A and additive B；The additive A is selected from sulfoxide compound, sulfone compound, sulfurous esters compound, methane-disulfonic acid
At least one of methylene ester；The additive B is selected from difluorophosphate or such as at least one of I compound represented of formula；
In formula I, R11、R12、R13It is respectively selected from substituted or unsubstituted C each independently1~20Alkyl, substitution do not take
The C in generation6~26Aryl, substituted or unsubstituted C1~20Alkoxy, substituted or unsubstituted C6~26Aryloxy group,Wherein, R ', R ", R " ' it is independent be respectively selected from it is substituted or unsubstituted
C1~20Alkyl；Or R11、R12、R13In two substituent groups connect to form 3~10 member rings, in 3~10 member ring also contain aerobic original
At least one of son or silicon atom；
Substituent group is selected from halogen, cyano, C1~4Alkyl.
Preferably, the additive B is selected from such as at least one of I A compound represented of formula；
In I A of formula, X, Y are independent to respectively indicate C, O or Si, and X, Y are not C simultaneously；R14Selected from substituted or unsubstituted
C1~6Alkylidene, substituent group are selected from halogen, cyano；
Preferably, the additive B is selected from such as at least one of I Aa compound represented of formula；
In I Aa of formula, R13' it is selected from substituted or unsubstituted C1~10Alkyl, substituted or unsubstituted C1~10Alkoxy, R14' choosing
From substituted or unsubstituted C2~4Alkylidene, substituent group are selected from halogen, cyano.
Preferably, R11、R12、R13It is independent to be respectively selected from substituted or unsubstituted C1~6It is alkyl, substituted or unsubstituted
C1~6Alkoxy；Substituent group is selected from halogen, cyano.
Preferably, the additive B is selected from trimethyl phosphate, triethyl phosphate, methyl-phosphoric acid dimethyl ester, methyl acid phosphate two
Ethyl ester or at least one of compound such as 1 structure of formula:
Preferably, the sulfoxide compound is selected from least one of compound as shown in II A of formula, the sulfone class chemical combination
Object is selected from least one of compound as shown in II B of formula, the sulfurous esters compound is selected from the compound as shown in II C of formula
At least one of,
Wherein, R21、R22It is respectively selected from substituted or unsubstituted C each independently1~20It is alkyl, substituted or unsubstituted
C2~20Alkenyl；
R23、R24It is respectively selected from substituted or unsubstituted C each independently1~20Alkyl, substituted or unsubstituted C2~20Alkene
Base or R23、R24Connection forms 4~10 member rings；
R25、R26It is respectively selected from substituted or unsubstituted C each independently1~20Alkyl, substituted or unsubstituted C2~20Alkene
Base or R25、R26Connection forms 5~10 member rings；
Substituent group is selected from halogen.
Preferably, the sulfoxide compound is selected from least one of dimethyl sulfoxide, diethyl sulfoxide；The sulfone class
Compound is preferably selected from least one of dimethyl sulfone, diethyl sulfone, sulfolane；The sulfurous esters compound preferentially selects
From ethylene sulfite, propylene sulfite, 4- methyl ethylene sulfite, dimethyl sulfite, sulfurous acid diethyl ester, sulfurous
At least one of sour methyl ethyl ester.
Preferably, the content of the additive A be the electrolyte gross mass 0.01%~3%, preferably 0.1%~
1%.
Preferably, the content of the additive B be the electrolyte gross mass 0.01%~3%, preferably 0.1%~
1%.
Preferably, the organic solvent is selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, carbon
Sour dipropyl, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, methyl butyrate, ethyl acetate, N-
At least one of methyl pyrrolidone, N-METHYLFORMAMIDE, N- methylacetamide, acetonitrile, methyl sulfide.
This application involves a kind of lithium ion batteries comprising electrolyte, positive plate, negative electrode tab, isolation film and package foil；Institute
The positive diaphragm that positive plate includes plus plate current-collecting body and is coated on plus plate current-collecting body is stated, negative electrode tab includes negative current collector and painting
Cathode membrane of the cloth on negative current collector；It is characterized in that, the electrolyte is the electrolyte of the application.
The technical solution of the application at least has following beneficial effect:
Viscosity is larger when the compound of the usually key containing S=O is used as solvent, will increase the DC internal resistance of battery, and single
Solely it is used as cathode film formation additive in use, SEI impedance can increase, such as dimethyl sulfoxide, dimethyl sulfone, SEI impedance after addition
It obviously increases；The compound of the key containing P=also viscosity with higher, the DC impedance that cannot reduce battery is used as solvent,
Separately as cathode film formation additive in use, SEI impedance is not substantially reduced, and it is more unstable to be formed by SEI, high temperature
It is lower to be easy to decompose, it is affected to the cycle performance of battery.The application is the study found that by the chemical combination of the key containing S=O in the application
After the compound (additive B) of object (additive A) and the key containing P=O is applied in combination, SEI impedance can be significantly reduced, inhibits to follow
The growth of SEI impedance during ring.Its reason can be considered following (but it is not limited to this): cathode film formation additive A and B application
After into lithium ion battery, the SEI phosphate particle formed containing P=O key compound reduction decomposition product is embedded in containing S=O
In the formation SEI of key compound, fine and close composite solid electrolyte interface (SEI) film is formed in negative terminal surface, increases SEI film
Ionic conductivity, and inhibit cyclic process in SEI impedance increase.
Specific embodiment
Combined with specific embodiments below, the application is further described.It should be understood that these embodiments are merely to illustrate the application
Rather than limitation scope of the present application.
This application involves a kind of electrolyte, the direct current resistance of the DC impedance and battery after circulation of fresh cells can reduce
It is anti-.The electrolyte includes organic solvent, electrolyte and additive, contains the additive as cathode film formation additive in additive
A and additive B；
Wherein, additive A is the compound containing S=O key, is selected from sulfoxide compound, sulfone compound, sulfite
At least one of class compound, sulfuric acid ester compound, methane-disulfonic acid methylene ester；
Additive B is the compound containing P=O key, is selected from difluorophosphate (LiPO2F2) and structure shown in formula I compound
It is at least one:
In formula I, R11、R12、R13It is respectively selected from substituted or unsubstituted C each independently1~20It is alkyl, substituted or unsubstituted
C6~26Aryl, substituted or unsubstituted C1~20Alkoxy, substituted or unsubstituted C6~26Aryloxy group,Wherein, R ', R ", R " ' it is independent be respectively selected from it is substituted or unsubstituted
C1~20Alkyl；Or R11、R12、R13In two substituent groups connect to form 3~10 member rings, in 3~10 member ring also contain aerobic original
At least one of son or silicon atom；
Substituent group is selected from halogen, cyano, C1~4Alkyl.
As a kind of improvement of the application electrolyte, when substituent group is straight chain or straight chain substituent, R11、R12、R13Respectively
Independently it is respectively selected from substituted or unsubstituted C1~6Alkoxy, substituted or unsubstituted phenyl,Wherein, R ', R ", R " ' it is independent be respectively selected from it is substituted or unsubstituted
C1~6Alkyl；
Substituent group is selected from halogen, C1~4Alkyl.
4 are preferably formed as when two substituent groups in substituent group connect cyclization as a kind of improvement of the application electrolyte
~10 member rings, more preferably 4~8 member rings of formation, most preferably formation five-membered ring or hexatomic ring.In the cyclic structure, a P original is removed
Outside son and carbon atom, it can also contain oxygen atom or silicon atom, preferably comprise 1~2 oxygen atom.
As a kind of improvement of the application electrolyte, additive B is selected from such as at least one of I A compound represented of formula；
In I A of formula, X, Y are independent to respectively indicate C, O or Si；
R14Selected from substituted or unsubstituted C1~10Alkylidene；Substituent group is selected from halogen, cyano.
For a kind of improvement of the application electrolyte, in I A of formula, X, Y are independent to respectively indicate C or O, R14Selected from taking
Generation or unsubstituted C2~6Alkylidene；Substituent group is selected from halogen, cyano.
As a kind of improvement of the application electrolyte, additive B in such as I Aa compound represented of formula at least one
Kind；
In I Aa of formula, R13' it is selected from substituted or unsubstituted C1~10Alkyl, substituted or unsubstituted C1~10Alkoxy, R14’
Selected from substituted or unsubstituted C2~4Alkylidene, substituent group are selected from halogen, cyano.
As a kind of improvement of the application electrolyte, in I Aa of formula, R13' it is selected from substituted or unsubstituted C1~6Alkyl,
R14' it is selected from substituted or unsubstituted C2~4Alkylidene；Substituent group is selected from halogen, cyano.
As a kind of improvement of the application electrolyte, R11、R12、R13It is independent be respectively selected from it is substituted or unsubstituted
C1~6Alkyl, substituted or unsubstituted C1~6Alkoxy；Substituent group is selected from halogen, cyano.
In the general formula of the application:
The alkyl that carbon atom number is 1~20, alkyl can be chain-like alkyl, can also be naphthenic base, on the ring of naphthenic base
Hydrogen can be replaced by alkyl, in the alkyl the preferred lower limit value of carbon atom number be 2,3,4,5, preferred upper limit value be 3,4,5,
6,8,10,12,14,16,18.Preferably, select carbon atom number for 1~12 alkyl, it is further preferred that selection carbon atom number
For 1~6 chain-like alkyl, carbon atom number is 3~8 naphthenic base, it is further preferred that select carbon atom number for 1~4 chain
Shape alkyl, the naphthenic base that carbon atom number is 5~7.It as the example of alkyl, can specifically enumerate: methyl, ethyl, n-propyl, different
Propyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, 2- Methyl pentyl, 3- first
Base-amyl, 1,1,2- trimethyl-propyl, 3,3 ,-dimethyl-butyl, heptyl, 2- heptyl, 3- heptyl, 2- methylhexyl, 3- first
Base hexyl, different heptyl, octyl, nonyl, decyl.
Carbon atom number be 6~26 aryl, such as phenyl, benzene alkyl, such as xenyl of the aryl at least containing a phenyl,
Condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base can also be replaced alkyl or alkenyl.Preferably, it selects
Select carbon atom number be 6~16 aryl, it is further preferred that select carbon atom number for 6~14 aryl, still more preferably
Ground, select carbon atom number for 6~9 aryl.As the example of aryl, can specifically enumerate: phenyl, benzyl, xenyl, to first
Phenyl, o-tolyl, tolyl.
It can be alkoxy when containing oxygen atom in the alkyl that the aforementioned carbon atom number being previously mentioned is 1~20.Preferably,
Select carbon atom number for 1~10 alkoxy, it is further preferred that select carbon atom number for 1~6 alkoxy, further
Preferably, select carbon atom number for 1~4 alkoxy.It as the example of alkoxy, can specifically enumerate: methoxyl group, ethoxy
Base, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, ring
Hexyloxy.
It can be aryloxy group when containing oxygen atom in the aryl that the aforementioned carbon atom number being previously mentioned is 6~26.Preferably,
Select carbon atom number for 6~16 aryloxy group, it is further preferred that select carbon atom number for 6~14 aryloxy group, further
Preferably, select carbon atom for 6~10 aryloxy group.As the example of aryloxy group, can specifically enumerate: phenoxy group, benzyloxy,
4- methylphenoxy, 3,5- dimethyl phenoxy, 4- methylbenzyloxy, 3- methylbenzyloxy, 2,6- diisopropyl benzyloxy, 1-
Naphthoxy.
The alkylidene that carbon atom number is 1~10 is linear chain or branched chain alkylidene, and carbon atom number is preferred in the alkylidene
Lower limit value is 2,3,4,5, and preferred upper limit value is 3,4,5,6,8,9.Preferably, select carbon atom number for 1~6 alkylidene.
It as the example of alkyl, can specifically enumerate: methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, Asia
Sec-butyl, pentylidene, hexylidene.
As a kind of improvement of the application electrolyte, when the substituent group in formula I is not cyclic, additive B is selected from following knot
At least one of structure formula:
Wherein, when the substituent group in formula I is linear chain or branched chain substituent group, additive B is further selected from following structural formula
At least one:
As a kind of improvement of the application electrolyte, when the substituent group cyclization in formula I, additive B is selected from flowering structure
At least one of formula:
As a kind of improvement of the application electrolyte, sulfoxide compound in the compound as shown in II A of formula at least
A kind of, sulfone compound is selected from least one of compound as shown in II B of formula, sulfurous esters compound is selected from such as II C of formula
At least one of shown compound, sulfuric acid ester compound are selected from least one of compound as shown in II D of formula；
Wherein, R21、R22It is respectively selected from substituted or unsubstituted C each independently1~20It is alkyl, substituted or unsubstituted
C2~20Alkenyl；
R23、R24It is respectively selected from substituted or unsubstituted C each independently1~20Alkyl, substituted or unsubstituted C2~20Alkene
Base or R23、R24Connection forms 4~10 member rings；
R25、R26It is respectively selected from substituted or unsubstituted C each independently1~20Alkyl, substituted or unsubstituted C2~20Alkene
Base or R25、R26Connection forms 5~10 member rings；
R27、R28It is respectively selected from substituted or unsubstituted C each independently1~20Alkyl, substituted or unsubstituted C2~20Alkene
Base ,-Si (R ')3Or R27、R28Connection forms 5~10 member rings；R ' is substituted or unsubstituted C1~6Alkyl；
Substituent group is selected from halogen.
Preferably, R21、R22It is respectively selected from substituted or unsubstituted C each independently1~6It is alkyl, substituted or unsubstituted
C2~6Alkenyl；R23、R24It is respectively selected from substituted or unsubstituted C each independently1~6Alkyl, substituted or unsubstituted C2~6Alkenyl；
R25、R26It is respectively selected from substituted or unsubstituted C each independently1~6Alkyl, substituted or unsubstituted C2~6Alkenyl；R27、R28Respectively
From being independently respectively selected from substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted C2~6Alkenyl ,-Si (R ')3；R ' is to replace
Or unsubstituted C1~6Alkyl.
Wherein, the ring that substituent group connects into each structural formula includes saturated rings and unsaturated ring.Preferably, in II C of formula
In, R25、R26Connection forms 5~10 member rings of saturation or 5~10 member rings with a carbon-carbon double bond；In II D of formula, R27、R28
Connection forms 5~10 member rings of saturation or 5~10 member rings with a carbon-carbon double bond.
As a kind of improvement of the application electrolyte,
Sulfoxide compound is selected from least one of following compound:
Sulfone compound is selected from least one of following compound:
Sulfurous esters compound is selected from least one of following compound:
Sulfuric acid ester compound is selected from least one of following compound:
As a kind of improvement of the application electrolyte, the content of additive A is the 0.01%~3% of electrolyte gross mass；
Upper limit value is 1%, 2%, 2.5%, 2.75%, and lower limit value is 0.05%, 0.1%, 0.5%.The content of additive A can be by
Any number in upper limit value and lower limit value constitutes its content.This is because when the content of additive A is lower than 0.01%,
It cannot be passivated negative terminal surface completely, so that it is anti-not can effectively prevent pair caused by the electronics transfer between electrolyte and electrode
It answers, reduces SEI impedance；And when additive A content is greater than 3%, thicker passivating film can be formed in positive electrode surface, cause lithium from
Sub- migration resistance increases, and increases the fever of battery.It is further preferred that the quality of the anode passivation protection agent in the electrolytic solution
Score is 0.1%~1%.
As a kind of improvement of the application electrolyte, the content of additive B is the 0.01%~3% of electrolyte gross mass；
Upper limit value is 1%, 2%, 2.5%, 2.75%, and lower limit value is 0.05%, 0.1%, 0.5%.The content of additive B can be by
Any number in upper limit value and lower limit value constitutes its content.This is because when the content of additive B is lower than 0.01%,
It cannot be passivated negative terminal surface completely, so that it is anti-not can effectively prevent pair caused by the electronics transfer between electrolyte and electrode
It answers, reduces SEI impedance；And when additive B content is greater than 2%, thicker passivating film can be formed in positive electrode surface, cause lithium from
Sub- migration resistance increases, and increases the fever of battery.It is further preferred that the quality of the anode passivation protection agent in the electrolytic solution
Score is 0.1%~1%.
As a kind of improvement of the application electrolyte, solvent be selected from ethylene carbonate, propylene carbonate, dimethyl carbonate,
Diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, butyric acid first
At least one of ester, ethyl acetate, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N- methylacetamide, acetonitrile, methyl sulfide.
As a kind of improvement of the application electrolyte, electrolyte optionally from organic bath or inorganic electrolyte at least
It is a kind of.
As a kind of improvement of the application electrolyte, contain at least one in fluorine element, boron element, P elements in electrolyte
Kind.
As a kind of improvement of the application electrolyte, electrolyte is selected from lithium hexafluoro phosphate LiPF6、LiBF4, LiBOB, double three
Fluoromethane sulfimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), bis- (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (be abbreviated as
At least one of LiFSI).
In order to achieve the above-mentioned object of the invention, present invention also provides a kind of lithium ion batteries comprising electrolyte, anode
Piece, negative electrode tab, isolation film and package foil；Positive plate includes plus plate current-collecting body and the positive diaphragm that is coated on plus plate current-collecting body,
Negative electrode tab includes negative current collector and the cathode membrane that is coated on negative current collector；Electrolyte is the electrolysis of any of the above-described paragraph
Liquid.
As a kind of improvement of the application lithium ion battery, positive diaphragm includes positive electrode active materials, binder and conduction
Agent.
As a kind of improvement of the application lithium ion battery, positive electrode active materials are optionally from cobalt acid lithium LiCoO2, lithium nickel manganese
The mixing of at least one of cobalt ternary material, phosphonic acids ferrous lithium, LiMn2O4 or cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material
Object.
As a kind of improvement of the application lithium ion battery, cathode membrane includes negative electrode active material, binder and conduction
Agent.
As a kind of improvement of the application lithium ion battery, negative electrode active material is carbon material and/or material, preferably
Graphite and/or silicon.
In following embodiments, comparative example and test example, used reagent, material and instrument are such as without special theory
It is bright, 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) are sub-
Sulfuric acid acrylic ester (PS), dimethyl sulfite (DMS), 4- methyl ethyl sulfate (PPS), sulfuric acid Asia propyl ester (PCS)；
Additive B: difluorophosphate (LiPO2F2), trimethyl phosphate (TMP), 1 compound represented of formula；
Lithium battery diaphragm: 16 microns thick of polypropylene isolation film (model A273 is provided by Celgard company).
Embodiment 1
Electrolyte 1~16 is prepared by the following method:
In drying shed, after EC and DEC is mixed, electrolyte is added, macrolides and additive is then added,
It is uniformly mixed, obtains electrolyte, wherein the additive amount of EC and DEC is the electrolysis so that EC and DEC weight ratio is EC:DEC=3:7
The additive amount of matter is so that LiPF6Molar concentration in the electrolytic solution is 1mol/L.
The preparation method of lithium ion battery:
Positive plate, lithium battery isolation membrane, negative electrode tab are folded in order, make lithium battery isolation membrane be in positive and negative plate it
Between play the role of isolation, then winding obtain naked battery core；Naked battery core is placed in outer packing foil, by the above-mentioned electrolysis prepared
Liquid is injected into the battery after drying, by processes such as Vacuum Package, standing, chemical conversion, shapings, obtains battery.
During above-mentioned preparation, the specific type and its dosage of used additive are as shown in table 1 below.Additive
Content be the weight percent that is calculated of the total weight based on electrolyte.
Comparative example electrolyte 1#~13# is prepared according to the method for embodiment, and difference is only that, the group of additive in electrolyte
At as shown in table 1 with additive amount.
Electrolysis additive combination and additive amount in table 1, embodiment and comparative example
Note: in table 1 above, "-" indicates not adding the substance corresponding in the table.
By lithium ion battery made from above-mentioned comparative example and embodiment, perform the following performance tests.
Test one, loop test
The lithium ion battery being prepared is subjected to following tests respectively:
At 25 DEG C, by lithium ion battery, with 0.5C constant-current charge to 4.35V, then constant-voltage charge to electric current is
0.05C, then carried out time so multiple circulation at this time to recycle for the first time with 0.5C constant-current discharge to 3.0V according to above-mentioned condition and filled
The capacity retention ratio after lithium ion battery recycles 300 times, every group of each 5 battery, wherein after circulation is calculated in electricity/electric discharge
Capacity retention ratio is calculated according to the following formula.Selected electrolyte and obtained dependence test number in each lithium ion battery
According to referring to table 2.
Capacity retention ratio after circulation=(discharge capacity after circulation/discharge capacity recycled for the first time) × 100%, circulation
The results are shown in Table 2 for test.
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, suspend mode 1 hour, then with
0.5C discharge 60 minutes (50%SOC), suspend mode 1 hour；Then with 0.1C electric discharge 10 seconds, voltage V when record end1, then with 1C
Electric discharge 1 second, voltage V when record end2, calculate battery DCR, DCR calculation formula: DCR=(V1-V2)/(I1C-I0.1C), unit is
mOhm.The DCR of battery after test fresh cells and 300 circulations, and calculate DCR growth rate, DCR Growth Rate Calculation formula are as follows:
Battery DCR × 100% after DCR growth rate=(battery DCR before battery DCR- is recycled after circulation)/circulation
Selected electrolyte and obtained relevant test data are referring to table 2 in each lithium ion battery.
The dependence test result of table 2, each comparative example and embodiment battery
It is possible thereby to learn, by electrolyte provided by the present application, after being applied in lithium ion battery, fresh cells are reduced
DCR, battery DCR increases after can further reducing circulation.In addition, when including simultaneously provided by the invention add in electrolyte
When adding agent A and additive B, additive A and additive B form stable SEI in negative terminal surface jointly, can be improved following for battery
Ring performance.
It is possible thereby to learn, electrolyte provided by the present application after being applied in lithium ion battery, can reduce lithium-ion electric
DCR increases in the DCR in pond and cyclic process, and does not influence the cycle performance of battery.
Embodiment 2
The present embodiment electrolyte is prepared according to the method for embodiment 1, and difference is only that, in electrolyte the composition of additive and
Additive amount is as shown in table 3.
Table 3:
The electrolyte of the present embodiment is prepared into lithium ion battery according to the method for embodiment 1, and according to the side in embodiment 1
Method detects the performance of battery, and the performance that detection obtains battery 17~33 is similar to above embodiments, as space is limited no longer
It repeats.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In use some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (11)
1. a kind of electrolyte, including organic solvent, electrolyte and additive, it is characterised in that: the additive includes additive A
And additive B；The content of the additive A is the 0.01%~3% of the electrolyte gross mass, the content of the additive B
It is the 0.01%~3% of the electrolyte gross mass, the additive A is selected from sulfoxide compound, sulfone compound, methane two
At least one of sulfonic acid methylene ester；The additive B is selected from difluorophosphate or such as at least one in I compound represented of formula
Kind；
In formula I, R11、R12、R13It is respectively selected from substituted or unsubstituted C each independently6~26It is aryl, substituted or unsubstituted
C1~20Alkoxy, substituted or unsubstituted C6~26Aryloxy group,Wherein, R ', R ",
R " ' is independent to be respectively selected from substituted or unsubstituted C1~20Alkyl；Or R11、R12、R13In two substituent groups connect to be formed
3~10 member rings also contain at least one of oxygen atom or silicon atom in 3~10 member ring；
Substituent group is selected from halogen, cyano, C1~4Alkyl.
2. electrolyte according to claim 1, which is characterized in that the additive B is selected from such as I A compound represented of formula
At least one of；
In I A of formula, X, Y are independent to respectively indicate C, O or Si, and X, Y are not C simultaneously；R14Selected from substituted or unsubstituted
C1~6Alkylidene, substituent group are selected from halogen, cyano.
3. electrolyte according to claim 2, which is characterized in that the additive B is selected from such as I Aa compound represented of formula
At least one of；
In I Aa of formula, R13' it is selected from substituted or unsubstituted C1~10Alkyl, substituted or unsubstituted C1~10Alkoxy, R14' selected from taking
Generation or unsubstituted C2~4Alkylidene, substituent group are selected from halogen, cyano.
4. electrolyte according to claim 1, which is characterized in that R11、R12、R13It is independent be respectively selected from substitution or
Unsubstituted C1~6Alkoxy；Substituent group is selected from halogen, cyano.
5. electrolyte according to claim 1, which is characterized in that the additive B is selected from methyl-phosphoric acid dimethyl ester, methyl
Diethyl phosphate or at least one of compound such as 1 structure of formula:
6. electrolyte according to claim 1, which is characterized in that the sulfoxide compound is selected to be changed as shown in II A of formula
Close at least one of object, the sulfone compound is selected from least one of compound as shown in II B of formula；
Wherein, R21、R22It is respectively selected from substituted or unsubstituted C each independently1~20Alkyl, substituted or unsubstituted C2~20Alkene
Base；
R23、R24It is respectively selected from substituted or unsubstituted C each independently1~20Alkyl, substituted or unsubstituted C2~20Alkenyl, or
R23、R24Connection forms 4~10 member rings；
Substituent group is selected from halogen.
7. electrolyte according to claim 1, which is characterized in that the sulfoxide compound is selected from dimethyl sulfoxide, two
At least one of ethyl-sulfoxide；The sulfone compound is preferably selected from dimethyl sulfone, diethyl sulfone, at least one in sulfolane
Kind.
8. electrolyte according to claim 1, which is characterized in that the content of the additive A is the total matter of the electrolyte
The 0.1%~1% of amount.
9. electrolyte according to claim 1, which is characterized in that the content of the additive B is the total matter of the electrolyte
The 0.1%~1% of amount.
10. electrolyte according to claim 1, which is characterized in that it is sub- that the organic solvent is selected from ethylene carbonate, carbonic acid
Propyl ester, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate,
Propyl propionate, methyl butyrate, ethyl acetate, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N- methylacetamide, acetonitrile, first sulphur
At least one of ether.
11. a kind of lithium ion battery comprising electrolyte, positive plate, negative electrode tab, isolation film and package foil；The positive plate packet
The positive diaphragm for including plus plate current-collecting body and being coated on plus plate current-collecting body, negative electrode tab include negative current collector and are coated on cathode collection
Cathode membrane on fluid；It is characterized in that, the electrolyte is electrolyte described in any one of claims 1 to 10.
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| CN106252716A (en) * | 2016-10-17 | 2016-12-21 | 东莞市凯欣电池材料有限公司 | A kind of safe lithium ion power battery electrolyte and lithium-ion-power cell |
| CN108242567A (en) * | 2016-12-26 | 2018-07-03 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN109075387B (en) * | 2017-01-20 | 2022-01-04 | 株式会社Lg化学 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
| CN107359368A (en) * | 2017-06-22 | 2017-11-17 | 武汉大学 | A kind of lithium battery electrolytes based on sulfuric acid ester additive |
| CN109037779A (en) * | 2018-09-19 | 2018-12-18 | 南通海嘉智能科技有限公司 | New energy battery electrolyte cathode film formation additive |
| CN110970621B (en) * | 2018-09-30 | 2021-02-26 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN109659617A (en) * | 2018-12-28 | 2019-04-19 | 蜂巢能源科技有限公司 | Lithium ion secondary battery and its electrolyte |
| CN112448033A (en) * | 2019-09-05 | 2021-03-05 | 杉杉新材料（衢州）有限公司 | High-voltage lithium ion battery electrolyte and long-cycle-life high-voltage lithium ion battery |
| CN110931868B (en) * | 2019-11-27 | 2022-04-15 | 惠州锂威新能源科技有限公司 | Non-aqueous electrolyte and lithium ion battery containing same |
| CN116130760A (en) * | 2020-12-23 | 2023-05-16 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device, and electronic device |
| CN114846668B (en) * | 2021-11-18 | 2024-02-23 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device comprising same and electronic device |
| CN114335726A (en) * | 2021-12-30 | 2022-04-12 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte and lithium ion battery containing same |
| CN116960467B (en) * | 2023-09-15 | 2024-02-20 | 宁德时代新能源科技股份有限公司 | Battery cell, battery and electricity utilization device |
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