CN105449279B - Nonaqueous electrolytic solution and the lithium ion battery for using the nonaqueous electrolytic solution - Google Patents
Nonaqueous electrolytic solution and the lithium ion battery for using the nonaqueous electrolytic solution Download PDFInfo
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- CN105449279B CN105449279B CN201511030610.7A CN201511030610A CN105449279B CN 105449279 B CN105449279 B CN 105449279B CN 201511030610 A CN201511030610 A CN 201511030610A CN 105449279 B CN105449279 B CN 105449279B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to field of lithium ion battery, specifically, are related to a kind of nonaqueous electrolytic solution and the lithium ion battery using the nonaqueous electrolytic solution.The nonaqueous electrolytic solution of the present invention, including non-aqueous organic solvent, lithium salts and additive, non-aqueous organic solvent contain at least one macrolide compounds, and additive includes at least one cathode film formation additive and at least one positive passivation protection agent；Positive passivation protection agent is selected from least one of 3,4 ethene dioxythiophenes, phosphonic acid cyclic acid anhydride compound, nitrile compound.The reduction potential of cathode film formation additive in nonaqueous electrolytic solution of the present invention is higher than macrolide compounds and can form stable cathode passivating film, and positive passivation protection agent can inhibit macrolide compounds in the oxygenolysis of anode；To which the over-charging of lithium ion battery can not only be improved, and the cycle performance of battery is not influenced.
Description
Technical field
The invention belongs to field of lithium ion battery, specifically, are related to a kind of nonaqueous electrolytic solution and use the nonaqueous electrolytic solution
Lithium ion battery.
Background technology
Lithium ion battery because have many advantages, such as it is higher than energy, have extended cycle life, self discharge it is small, be 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 is various, requires the security performance of battery higher and higher.For example, in order to ensure the charging safety of electronic product, it is desirable that battery core
Possess the anti-overcharge performance of higher.
Studies have shown that macrolide compounds are less than the oxidizing potential of conventional carbonic ester and oxidation reaction in anode due to it
Surface forms insulating layer and separates electric current, to be obviously improved the over-charging of battery, but due to its excessively high reduction potential shadow
It rings EC, FEC etc. and forms prodigious, the unstable cathode passivating film (SEI) of impedance, influence the cycle performance (Journal of battery
of power sources,2008,183,755-760).And the oxidizing potential of macrolide compounds is also below conventional carbonic acid
Ester can aoxidize in cyclic process in anode, and product will increase the impedance of battery, influence the cycle performance of battery.Improve containing ring
The cycle performance of lactone compound electrolyte needs to find suitable cathode film formation additive and positive passivation protection agent.
In consideration of it, special propose the present invention.
Invention content
The first invention of the present invention, which is designed to provide a kind of electrolyte, can be obviously improved the over-charging of battery, and not
Influence the cycle performance of battery.
The second goal of the invention of the present invention is to provide a kind of lithium ion battery of the nonaqueous electrolytic solution using the present invention.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is：
The present invention relates to a kind of nonaqueous electrolytic solutions, including non-aqueous organic solvent, lithium salts and additive, non-aqueous organic solvent to contain
It includes at least one cathode film formation additive and at least one positive passivation protection to have at least one macrolide compounds, additive
Agent；Positive passivation protection agent is selected from 3,4- ethene dioxythiophenes, the phosphonic acid cyclic acid anhydride compound as shown in formula I, as shown in II institute of formula
At least one of nitrile compound：
Wherein, in formula I, R11、R12、R13It is each independently selected from C1~6Alkyl, substituted or unsubstituted phenyl；In formula II
In, R14, R15And R16Independently selected from C1-5Alkylidene, substituted or unsubstituted phenylene；Substituent group is C1-3Alkyl.
Preferably, the type I compound be selected from triphenyl phosphonic acids cyclic anhydride, tripropyl phosphonic acids cyclic anhydride, triethyl group phosphonic acids cyclic anhydride,
At least one of trimethyl phosphonic acids cyclic anhydride.
Preferably, II compound of the formula is selected from least one of II a of formula, II b of formula, II c of formula：
Preferably, the cathode film formation additive be selected from vinylene carbonate, vinylethylene carbonate, succinic anhydride,
Maleic anhydride, LiBF4 (LiBF4), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), 1,3- third
At least one of sultone, ethyl sulfate.
Preferably, the macrolide compounds are selected from formula III, at least one of formula IV：
Wherein, in formula III, the integer that n is 1~3, R1~R6It is each independently selected from hydrogen atom, halogen atom, substitution or not
Substituted C1~10Alkyl, substituent group are selected from F, Cl, Br.Preferably, III compound of the formula be selected from gamma-butyrolacton, δ-butyrolactone,
At least one of 6-caprolactone, III a of formula, III b of formula, III c of formula：
Preferably, mass fraction of the positive passivation protection agent in nonaqueous electrolytic solution is 0.1%~10%, preferably
0.5%~5%.
Preferably, mass fraction of the cathode film formation additive in nonaqueous electrolytic solution is 0.1%~20%, preferably
0.5%~8%.
Preferably, the solvent also includes ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid
Dipropyl, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, methyl butyrate, ethyl acetate, N- first
Base pyrrolidones, N-METHYLFORMAMIDE, N- methylacetamides, acetonitrile, sulfolane, dimethyl sulfoxide (DMSO), glycol sulfite, sulfurous
It is one or more in sour Asia propyl ester, methyl sulfide, sulfurous acid diethyl ester, dimethyl sulfite.
The invention further relates to a kind of lithium ion battery, including electrolyte, positive plate, negative plate, isolation film and package foil, institutes
State the nonaqueous electrolytic solution that electrolyte is the present invention.
Specific implementation mode
The present invention provides a kind of nonaqueous electrolytic solution, including non-aqueous organic solvent, lithium salts and additive, non-aqueous organic solvents
Containing at least one macrolide compounds, additive includes at least one reduction potential cathode higher than the macrolide compounds
Film for additive and at least one positive passivation protection agent.
The nonaqueous electrolytic solution of the present invention overcomes macrolide compounds since reduction potential is excessively high to influence EC, FEC
Etc. forming the cathode passivating film (SEI) that impedance is prodigious, unstable.Firstly, it is necessary to using reduction potential higher than EC's and can
Form the film for additive for stablizing SEI；Secondly, it needs using the positive passivation protection agent that can be passivated positive oxidation activity, suppression
Macrolide compounds processed are in positive oxygenolysis, so as to improve the cycle performance containing macrolide compounds electrolyte.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, additive includes at least one positive passivation protection agent, specifically
In the compound of phosphonic acids cyclic anhydride selected from 3,4- ethene dioxythiophenes, with structure shown in formula I, the nitrile compound with II structure of formula
It is at least one：
Wherein, in formula I, R11、R12、R13It is each independently selected from C1~6Alkyl, substituted or unsubstituted phenyl；
In formula II, R14, R15And R16Independently selected from C1-5Alkylidene, substituted or unsubstituted phenylene；Substituent group is
C1-3Alkyl.
The preferred upper limit value of the carbon atom number of abovementioned alkyl or alkylidene is followed successively by 5,4,3；For example, the preferred carbon of alkyl is former
Subnumber is 1~5, and most preferably 1~3.Alkyl can be alkyl group or naphthenic base：Alkyl group is comprising straight chained alkyl and with branch
Alkyl；Naphthenic base is the saturated alkyl containing alicyclic structure.
As the example of alkyl, can specifically enumerate：It is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, different
Butyl, sec-butyl, tertiary butyl, cyclobutyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, cyclopenta, 2,2- dimethyl propyls,
1- ethyl propyls, 1- methyl butyls, 2- methyl butyls, n-hexyl, isohesyl, 2- hexyls, 3- hexyls, cyclohexyl, 2- methylpents
Base, 3- methyl amyls, 1,1,2- thmethylpropyl, 3,3- dimethylbutyls.
As the example of alkylidene, can specifically enumerate：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- ring third
Base, sub- normal-butyl, isobutylene, sub- sec-butyl, sub- tertiary butyl, sub- cyclobutyl, sub- n-pentyl, isoamylidene, sub- different tertiary pentyl,
Sub- different neopentyl, sub- different cyclopenta, 2,2- dimethylpropylidenes, 1- ethylisopropyls base, 1- methyl-isobutyls, 2- methyl tert-butyls
Base.
Phenylene can be 1,2- phenylenes, 1,3- phenylenes or Isosorbide-5-Nitrae-phenylene, and preferably Isosorbide-5-Nitrae-phenylene.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, II compound of formula in II a of formula, II b of formula, II c of formula extremely
Few one kind：
As a kind of improvement of nonaqueous electrolytic solution of the present invention, positive passivation protection agent is preferably tripropyl phosphonic acids cyclic anhydride, 3,
At least one of 4- ethene dioxythiophenes, II a compounds represented of formula.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, mass fraction of the positive passivation protection agent in nonaqueous electrolytic solution
It is 0.1%~10%.This is because when the content of positive passivation protection agent is less than 0.05%, it cannot be passivated positive table completely
Face, to not can effectively prevent the side reaction caused by the electronics transfer between electrolyte and electrode；And when positive passivation protection
When agent content is more than 10%, thicker passivating film can be formed in positive electrode surface, causes lithium ion mobility resistance to increase, is unfavorable for following
The positive interface stability of battery during ring.It is further preferred that the anode passivation protection agent is in nonaqueous electrolytic solution
Mass fraction is 0.5%~5%.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, non-when tripropyl phosphonic acids cyclic anhydride is as positive passivation protection agent
Mass fraction in water electrolysis liquid is 0.05%~3%, it is further preferred that tripropyl phosphonic acids cyclic anhydride is in nonaqueous electrolytic solution
Mass fraction is 0.1%~2%.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, when 3,4-rthylene dioxythiophene is as positive passivation protection agent
Mass fraction in nonaqueous electrolytic solution is 0.05%~3%, it is further preferred that 3,4-rthylene dioxythiophene is in nonaqueous electrolytic solution
In mass fraction be 0.1%~0.5%.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, when II compound represented of formula is as positive passivation protection agent
Mass fraction in nonaqueous electrolytic solution is 0.05%~3%, it is further preferred that II compound represented of formula is in nonaqueous electrolytic solution
In mass fraction be 0.1%~2%.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, the additive includes at least one reduction potential than the ring
The high cathode film formation additive of lactone compound, is chosen in particular from vinylene carbonate (VC), vinylethylene carbonate, succinic acid
Acid anhydride, maleic anhydride, LiBF4 (LiBF4), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB), 1,3-
Propane sultone (PS) and ethyl sulfate (DTD).
As a kind of improvement of nonaqueous electrolytic solution of the present invention, the cathode film formation additive is preferably vinylene carbonate
(VC), LiBF4 (LiBF4), di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB) and 1,3- propane sulphurs
Acid lactone (PS).
As a kind of improvement of nonaqueous electrolytic solution of the present invention, quality of the cathode film formation additive in nonaqueous electrolytic solution
Score is 0.1%~20%.This is because when the content of cathode film formation additive is less than 0.05%, it cannot be in negative terminal surface shape
At complete SEI films, to not can effectively prevent the side reaction caused by the electronics transfer between electrolyte and electrode；And when negative
When pole film for additive content is more than 20%, thicker SEI films can be formed in negative terminal surface, lithium ion mobility resistance is caused to increase
Greatly, it is unfavorable for the cathode interface stability of battery in cyclic process.It is further preferred that the cathode film formation additive is non-aqueous
Mass fraction in electrolyte is 0.5%~8%.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, when vinylene carbonate (VC) is used as cathode film formation additive
Mass fraction in nonaqueous electrolytic solution is 0.05%~3%, it is further preferred that mass fractions of the VC in nonaqueous electrolytic solution is
0.1%~1.5%.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, LiBF4 (LiBF4) be used as cathode film formation additive when
Mass fraction in nonaqueous electrolytic solution is 0.05%~1%, it is further preferred that LiBF4Quality in nonaqueous electrolytic solution
Score is 0.1%~0.5%.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, di-oxalate lithium borate (LiBOB) is used as cathode film formation additive
When mass fraction in nonaqueous electrolytic solution be 0.05%~1%, it is further preferred that matter of the LiBOB in nonaqueous electrolytic solution
It is 0.1%~0.5% to measure score.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, difluorine oxalic acid boracic acid lithium (LiDFOB) is added as cathode film formation
Mass fraction when agent in nonaqueous electrolytic solution is 0.05%~1%, it is further preferred that LiDFOB is in nonaqueous electrolytic solution
Mass fraction is 0.1%~0.5%.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, 1,3- propane sultone (PS) is used as cathode film formation additive
When mass fraction in nonaqueous electrolytic solution be 0.05%~7%, it is further preferred that quality of the PS in nonaqueous electrolytic solution point
Number is 0.1%~5%.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, contain shown in formula III or formula IV in the non-aqueous organic solvent
At least one of macrolide compounds：
Wherein, in formula III, the integer that n is 1~3, R1~R6It is each independently selected from hydrogen atom, halogen atom, substitution or not
Substituted C1~10Alkyl, substituent group are selected from F, Cl, Br.
As the example of VI compound represented of formula V and formula, can specifically enumerate：Gamma-butyrolacton, δ-butyrolactone, ε-oneself
Lactone, III a of formula, III b of formula, III c of formula, compound shown in formula IV：
As a kind of improvement of nonaqueous electrolytic solution of the present invention, mass fraction of the macrolide compounds in nonaqueous electrolytic solution is
0.1%~40%.This is because when the content of cyclic lactone chemical combination is less than 0.1%, cannot be formed in positive electrode surface complete exhausted
Velum, to cannot effectively block the over-charging for overcharging electric current improvement battery；And when macrolide compounds content is more than 40%
When, electrolysis fluid viscosity is too big, and lithium ion mobility resistance is caused to increase, and positive passivation protection film effectively can not inhibit electrolyte to exist
The oxidation reaction of positive electrode surface.It is further preferred that mass fraction of the cathode film formation additive in nonaqueous electrolytic solution be 1%~
30%.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, solvent also includes ethylene carbonate, propylene carbonate, carbonic acid two
Methyl esters, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, fourth
Sour methyl esters, ethyl acetate, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N- methylacetamides, acetonitrile, sulfolane, dimethyl are sub-
At least one of sulfone, glycol sulfite, sulfurous acid Asia propyl ester, methyl sulfide, sulfurous acid diethyl ester, dimethyl sulfite.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, lithium salts is optionally from least one in organic lithium salt or inorganic lithium salt
Kind.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, in lithium salts containing in fluorine element, boron element, P elements at least
It is a kind of.
As a kind of improvement of nonaqueous electrolytic solution of the present invention, lithium salts is selected from lithium hexafluoro phosphate LiPF6, double fluoroform sulphonyl
Imine lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), bis- (fluorine sulphonyl) imine lithium Li (N (SO2F)2) in (being abbreviated as LiFSI)
It is at least one.
In order to achieve the above-mentioned object of the invention, the present invention also provides a kind of lithium ion batteries comprising electrolyte, anode
Piece, negative plate, isolation film and package foil；Electrolyte is the nonaqueous electrolytic solution of the present invention.
As a kind of improvement of lithium ion battery of the present invention, positive diaphragm includes positive electrode active materials, binder and conduction
Agent.
As a kind of improvement of lithium ion battery of the present invention, positive electrode active materials are optionally from cobalt acid lithium LiCoO2, lithium nickel manganese
The mixing of at least one of cobalt ternary material, LiFePO 4, LiMn2O4 or cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material
Object.
As a kind of improvement of lithium ion battery of the present invention, cathode membrane includes negative electrode active material, binder and conduction
Agent.
As a kind of improvement of lithium ion battery of the present invention, the negative electrode active material is in graphite, silicon, silicide
It is one or more, wherein silicon can be selected from nano silicon particles, silicon nanowires, nano-tube, silicon thin film, 3D porous structures silicon and
Hollow porous silicon it is one or more, but be not limited to above-mentioned enumerated silicon.
In above-mentioned lithium ion battery, the specific type of the lithium battery diaphragm is not exposed to specific limitation, can be selected
Any conventional lithium battery diaphragm material used in lithium ion battery, such as polyethylene, polypropylene, Kynoar and above-mentioned
The multilayer complex films of polyethylene, polypropylene, Kynoar, but it is not limited to above-mentioned enumerated lithium battery diaphragm material.
The preparation method of lithium ion battery provided by the present application is well known in the present art, can be by existing lithium ion
Battery preparation method manufactures lithium ion battery provided herein.
Compared with prior art, the present invention provides the over-chargings that a kind of electrolyte can be obviously improved battery, and not
Influence the cycle performance of battery.
The application is further described below by way of specific example.But these examples are only exemplary, not to this
The protection domain of application constitutes any restrictions.
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), propene carbonate (being abbreviated as PC), lithium salts：
LiPF6。
Compound：Vinylene carbonate (VC), LiBF4, LiBOB, LiDFOB, 1,3- propane sultone (PS), 3 third
Base phosphonic acids cyclic anhydride (T3P), 3,4-rthylene dioxythiophene (EDOT), II a compounds of formula, gamma-butyrolacton (GBL), δ-butyrolactone, ε-
Caprolactone, III a of formula, III b of formula, III c of formula, IV a compounds represented of formula：
Lithium battery diaphragm：16 microns thick of polypropylene isolation film (model A273 is provided by Celgard companies).
The preparation of embodiment electrolyte
Electrolyte is prepared by the following method：
In drying shed, after EC, PC and DEC are mixed, lithium salts is added, macrolide compounds and additive is then added,
It is uniformly mixed, obtains electrolyte, wherein the additive amount of EC, PC and DEC are so that EC, PC and DEC weight ratio are EC:PC:DEC
=1:1:3, the additive amount of lithium salts is so that the molar concentrations of LiPF6 in the electrolytic solution are 1mol/L.
During above-mentioned preparation, the specific type and its dosage of used macrolide compounds and additive are as follows
Shown in table 1.
Electrolysis additive formula and additive amount in table 1, embodiment (1#~25#) and comparative example (D1~D8)
Lithium ion battery made from each comparative example of the present invention and embodiment will be tested for the property by experiment below.
Test one, loop test
The lithium ion battery being prepared respectively is subjected to following tests：
At 25 DEG C, by lithium ion battery, with 0.5C constant-current charges to 4.35V, then constant-voltage charge to electric current is
0.05C, then filled into so many cycle of places according to above-mentioned condition at this time to recycle for the first time with 0.5C constant-current discharges to 3.0V
Electricity/electric discharge, calculate separately obtain lithium ion battery recycle 50 times, 100 times, 200 times and 300 times after capacity retention ratio, every group
Each 5 batteries, wherein the capacity retention ratio after cycle is calculated according to the following formula.Selected electricity in each lithium ion battery
Liquid and obtained relevant test data are solved referring to table 2.
Capacity retention ratio after cycle=(discharge capacity of corresponding cycle/discharge capacity recycled for the first time) × 100%, it follows
The results are shown in Table 2 for ring test.
Capacity retention ratio (%) after table 2, cycle
From the related data in above-mentioned table 2 it is known that compared to battery D1~D5, battery 1~19 respectively pass through 50 times,
After 100 times, 200 times, 300 times recycle, higher capacity retention ratio is all had.By D7, D8 it is found that only addition cathode film formation addition
One kind in agent or positive passivation protection agent, it is poor to the capacity retention ratio effect for keeping battery.
It is possible thereby to learn, by electrolyte provided by the present application, after being applied in lithium ion battery, battery can not be influenced
Cycle performance, further improve cycle performance of the battery under the high voltage of 4.35V or more.In addition, when same in electrolyte
When including cathode film formation additive provided by the invention and positive passivation protection agent, the cycle of battery can be further increased
Performance particularly further improves cycle performance of the battery under the high voltage of 4.35V or more.
Test two overcharges test
At 25 DEG C, lithium ion battery is respectively taken 5 constant voltages with the constant current of 1C and 10V start to charge up, directly
It to overcharging, while measuring the peak temperature of lithium ion battery and reaching the time used in peak temperature, and observe and overcharge
The state of lithium ion battery afterwards.Overcharging test, the results are shown in Table 3.
The result after overcharging test of 25 DEG C of batteries made from table 3, each comparative example and embodiment
From the correlated results in above-mentioned table 3 it is known that compared to battery D1, D4, D5 and D6, overcharge test and presented
State is compared, and after the battery of the electrolyte containing macrolide compounds overcharges test, generally speaking battery has been not susceptible to
The phenomenon of fire.
It is possible thereby to learn, electrolyte provided by the present application, after being applied in lithium ion battery, lithium-ion electric can be improved
The over-charging in pond, and the cycle performance of battery is not influenced.
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 in specific implementation modes 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 used some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of nonaqueous electrolytic solution, including non-aqueous organic solvent, lithium salts and additive, it is characterised in that：It is described non-aqueous organic molten
Agent contains at least one macrolide compounds, and the additive includes at least one cathode film formation additive and at least one anode
Passivation protection agent；The anode passivation protection agent be selected from 3,4- ethene dioxythiophenes, the phosphonic acid cyclic acid anhydride compound as shown in formula I,
At least one of nitrile compound as shown in II institute of formula：
Wherein, in formula I, R11、R12、R13It is each independently selected from C1~6Alkyl, substituted or unsubstituted phenyl；In formula II,
R14, R15And R16Independently selected from C1-5Alkylidene, substituted or unsubstituted phenylene；Substituent group is C1-3Alkyl；
Mass fraction of the macrolide compounds in the nonaqueous electrolytic solution is 0.1%~40%；
The macrolide compounds are selected from formula III, at least one of formula IV：
Wherein, in formula III, the integer that n is 1~3, R1~R6It is each independently selected from hydrogen atom, halogen atom, substitution or unsubstituted
C1~10Alkyl；Substituent group is selected from F, Cl, Br；The cathode film formation additive includes vinylene carbonate and other cathode film formations
Additive, other described cathode film formation additives are selected from vinylethylene carbonate, succinic anhydride, maleic anhydride, tetrafluoro boric acid
At least one of lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, 1,3- propane sultones, ethyl sulfate.
2. nonaqueous electrolytic solution according to claim 1, which is characterized in that the type I compound is selected from triphenyl phosphonic acid cyclic
At least one of acid anhydride, tripropyl phosphonic acids cyclic anhydride, triethyl group phosphonic acids cyclic anhydride, trimethyl phosphonic acids cyclic anhydride.
3. nonaqueous electrolytic solution according to claim 1, which is characterized in that II compound of the formula be selected from II a of formula, II b of formula,
At least one of II c of formula：
4. nonaqueous electrolytic solution according to claim 1, which is characterized in that III compound of the formula is selected from gamma-butyrolacton, δ-
At least one of butyrolactone, 6-caprolactone, III a of formula, III b of formula, III c of formula；
5. nonaqueous electrolytic solution according to claim 1, which is characterized in that the anode passivation protection agent is in nonaqueous electrolytic solution
In mass fraction be 0.1%~10%.
6. according to the nonaqueous electrolytic solution described in claim 5, which is characterized in that the anode passivation protection agent is in nonaqueous electrolytic solution
Mass fraction be 0.5%~5%.
7. nonaqueous electrolytic solution according to claim 1, which is characterized in that the cathode film formation additive is in nonaqueous electrolytic solution
In mass fraction be 0.1%~20%.
8. nonaqueous electrolytic solution according to claim 7, which is characterized in that the cathode film formation additive is in nonaqueous electrolytic solution
In mass fraction be 0.5%~8%.
9. electrolyte according to claim 1, which is characterized in that the solvent also includes ethylene carbonate, polypropylene carbonate
Ester, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, third
Propyl propionate, methyl butyrate, ethyl acetate, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N- methylacetamides, acetonitrile, ring fourth
In sulfone, dimethyl sulfoxide (DMSO), glycol sulfite, sulfurous acid Asia propyl ester, methyl sulfide, sulfurous acid diethyl ester, dimethyl sulfite
It is one or more.
10. a kind of lithium ion battery comprising electrolyte, positive plate, negative plate, isolation film and package foil, which is characterized in that institute
State electrolyte nonaqueous electrolytic solution as claimed in any one of claims 1 to 9.
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| CN105826606B (en) * | 2016-05-16 | 2020-02-18 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery containing same |
| CN106252715A (en) * | 2016-09-30 | 2016-12-21 | 合肥国轩高科动力能源有限公司 | A kind of high-temperature electrolyte of lithium ion battery |
| CN106410279A (en) * | 2016-11-30 | 2017-02-15 | 宁德时代新能源科技股份有限公司 | Electrolyte and secondary battery |
| KR102542965B1 (en) * | 2018-02-16 | 2023-06-14 | 다이킨 고교 가부시키가이샤 | Electrolysis solution, electrochemical device, lithium-ion secondary battery, and module |
| CN108461808A (en) * | 2018-03-21 | 2018-08-28 | 上海力信能源科技有限责任公司 | A kind of lithium ion battery of high-energy density and preparation method thereof |
| CN110299561B (en) * | 2018-03-21 | 2022-02-08 | 比亚迪股份有限公司 | Non-aqueous electrolyte and lithium ion battery containing same |
| DE102018006379A1 (en) * | 2018-08-11 | 2020-02-13 | Forschungszentrum Jülich GmbH | Liquid electrolytes comprising organic carbonates for applications in lithium-ion, lithium-metal and lithium-sulfur batteries |
| CN109841903A (en) * | 2019-03-29 | 2019-06-04 | 山东海容电源材料股份有限公司 | A kind of high voltage nonaqueous electrolytic solution of resistance to combustion |
| CN114024035B (en) * | 2021-10-25 | 2022-08-16 | 珠海冠宇电池股份有限公司 | Battery with a battery cell |
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| CN102522590B (en) * | 2011-12-26 | 2014-09-17 | 华为技术有限公司 | Non-aqueous organic electrolyte, lithium ion secondary battery containing non-aqueous organic electrolyte, preparation method of lithium ion secondary battery and terminal communication equipment |
| CN103794819A (en) * | 2014-01-17 | 2014-05-14 | 苏州氟特电池材料有限公司 | Nonaqueous electrolyte containing sulfonyl fluoride imidogen lithium salt as well as application of electrolyte |
| CN104332653B (en) * | 2014-09-01 | 2017-03-01 | 东莞新能源科技有限公司 | A kind of nonaqueous electrolytic solution and the lithium ion battery using this electrolyte |
| CN104466247B (en) * | 2014-12-16 | 2018-05-08 | 东莞新能源科技有限公司 | A kind of lithium ion battery of nonaqueous electrolytic solution and the application electrolyte |
| CN104577200A (en) * | 2015-02-06 | 2015-04-29 | 宁德新能源科技有限公司 | Electrolyte additive and application thereof |
| CN104752769A (en) * | 2015-04-10 | 2015-07-01 | 宁德新能源科技有限公司 | Non-aqueous electrolyte and lithium ion battery utilizing same |
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