CN105762410B - A kind of nonaqueous electrolytic solution and the lithium ion battery using the nonaqueous electrolytic solution - Google Patents
A kind of nonaqueous electrolytic solution and the lithium ion battery using the nonaqueous electrolytic solution Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- 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
This application involves 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 application includes non-aqueous organic solvent, lithium salts and additive, and additive contains methane-disulfonic acid methylene ester compounds and alkoxy ester type compound.The synergistic effect of alkoxy ester type compound and methane-disulfonic acid methylene ester compounds, stable passivating film is respectively formed in positive and negative pole surface, so as to significantly improve the high-temperature storage performance and cycle performance of battery.
Description
Technical field
This application involves 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 expansion character under the discharge-rate, battery life and hot conditions of battery higher and higher.For example, battery needs
The service life etc. of battery is improved in the case of big multiplying power repid discharge in the storage of high temperature long-time and battery.
Discharge-rate, service life and the high-temperature storage performance of lithium ion battery are influenced by factors, wherein electrolyte
As the important component of lithium ion battery, there is significant impact to it.The kinetics of battery can be improved by electrolyte
Can, reduce big multiplying power polarization, positive and negative anodes interface stability improves discharge-rate, longevity to reach during cycle and high temperature storage
Life, the purpose of high temperature storage.
Invention content
The primary goal of the invention of the application is to propose a kind of nonaqueous electrolytic solution, to significantly provide lithium-ion electric tank discharge
Multiplying power improves cycle performance of lithium ion battery and high-temperature storage performance.
The second goal of the invention of the application is to propose the lithium ion battery containing the nonaqueous electrolytic solution.
In order to complete the purpose of the application, the technical solution used for：
This application involves a kind of nonaqueous electrolytic solution, including non-aqueous organic solvent, lithium salts and additive, the additive contains
Methane-disulfonic acid methylene ester compounds and alkoxy ester type compound.
Preferably, the structural formula of the alkoxy ester type compound is as shown in formula I：
Wherein, R1、R4It is separate to be respectively selected from substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted C6~26
Aryl；
R2、R3It is separate to be respectively selected from hydrogen atom, halogen atom, substituted or unsubstituted C1~6Alkyl, substitution or not
Substituted C1~6Alkylene, and R2、R3In at least one substituent group be selected from substituted or unsubstituted C1~6Alkyl；
Substituent group is selected from halogen, and the halogen is selected from F or Cl.
Preferably, R1、R4It is separate to be respectively selected from substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted benzene
Base；R2、R3It is separate to be respectively selected from halogen atom, substituted or unsubstituted C1~6Alkyl, and R2、R3In at least one take
Dai Ji is selected from substituted or unsubstituted C1~6Alkyl.
Preferably, the alkoxy ester chemical combination object is selected from least one of following compound：
Preferably, the structural formula of the methane-disulfonic acid methylene ester compounds is as shown in formula II：
Preferably, mass percentage content of the methane-disulfonic acid methylene ester compounds in nonaqueous electrolytic solution is
0.05%~3%, preferably 0.1%~2%.
Preferably, mass percentage content of the alkoxy ester type compound in nonaqueous electrolytic solution be 0.01%~
10%, preferably 0.1%~5%.
Preferably, it is 1~8 and the compound containing at least one ester group that the non-aqueous organic solvent, which is selected from carbon atom number,；
Preferably, the non-aqueous organic solvent is selected from ethylene carbonate, propene carbonate, butylene, fluorinated ethylene carbonate, carbon
Sour methyl ethyl ester, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone, third
At least one of sour methyl esters, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate, ethyl butyrate.
Preferably, the lithium salts is optionally from least one of organic lithium salt or inorganic lithium salt；Preferably, the lithium salts choosing
From lithium hexafluoro phosphate LiPF6, double trifluoromethanesulfonimide lithiums, bis- (fluorine sulphonyl) imine lithiums, di-oxalate lithium borate, difluoro oxalate
At least one of lithium borate.
The application further relates to a kind of lithium ion battery comprising electrolyte, positive plate, negative plate, isolation film and package foil；
The positive plate includes plus plate current-collecting body and the positive diaphragm that is coated on plus plate current-collecting body, negative plate include negative current collector and
The cathode membrane being coated on negative current collector；The electrolyte is the nonaqueous electrolytic solution of the application.
The technical solution of the application at least has following beneficial effect：
Research shows that alkoxy ester type compound reduction potential substantially 2.0V vs.Li/Li+, it can be in battery core cathode table
Face forms fine and close SEI film (SEI), decomposition of the solvent in cathode is effectively reduced, to the cycle performance of battery
It is very useful；This is because alkoxy and the alkoxy lithium class compound that lithium is formed be covered in negative terminal surface it is opposite with lithium alkylide more
Difficulty is dissolved by the solvent, and SEI more stablizes.Methane-disulfonic acid methylene ester compounds easily form relatively stable alkoxy in positive electrode surface
Lithium or alkyl sulfonic acid lithium compound form effective interfacial film (CEI), and the passivation membrane impedance formed is smaller, while can be effective
It prevents positive electrode that side reaction occurs in positive electrode surface with electrolyte, and can effectively reduce positive interface in cyclic process
The increase of impedance.After alkoxy ester type compound and methane-disulfonic acid methylene ester compound combination use, by their collaboration
Effect is relatively stablized in the passivating film that positive and negative pole surface is formed, and positive passivating film can prevent positive electrode such as Mn, Co
Dissolution prevents O from discharging, and makes cell expansion to prevent O that oxidation aerogenesis occurs with electrolyte；It is embedded many containing F in cathode passivating film
Ingredient, be conducive to increase SEI films ionic conductivity, so that the movement of lithium ion is become more smooth, improve coulombic efficiency and
Battery membrane impedance increase in cyclic process is also smaller, and battery capacity decaying is small.Simultaneously as SEI and CEI effective and stablize
In the presence of and significantly improve the high-temperature storage performance and cycle performance of battery.
With reference to specific embodiment, the application is expanded on further.It should be understood that these embodiments are merely to illustrate the application
Rather than limitation scope of the present application.
Specific implementation mode
This application provides one kind capable of significantly providing lithium ion battery discharge-rate, improves cycle performance of lithium ion battery
Contain methane-disulfonic acid with the nonaqueous electrolytic solution of high-temperature storage performance, including non-aqueous organic solvent, lithium salts and additive, additive
Methylene ester compounds and at least one alkoxy ester type compound.
As a kind of improvement of the application nonaqueous electrolytic solution, the structural formula of alkoxy ester type compound is as shown in formula I：
Wherein, R1、R4It is separate to be respectively selected from substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted C6~26
Aryl；
R2、R3It is separate to be respectively selected from hydrogen atom, halogen atom, substituted or unsubstituted C1~6Alkyl, substitution or not
Substituted C1~6Alkylene, and R2、R3In at least one substituent group be selected from substituted or unsubstituted C1~6Alkyl；
Substituent group is selected from halogen, and the halogen is selected from F or Cl.
In this application：
The alkyl that carbon atom number is 1~6, alkyl can be chain-like alkyl or naphthenic base, be located on the ring of naphthenic base
Hydrogen can be replaced by alkyl, and the preferred lower limiting value of carbon atom number is 2,3 in the alkyl, and preferred upper limit value is 4,5,6.It is preferred that
Ground, select carbon atom number for 1~6 chain-like alkyl, it is further preferred that select carbon atom number for 1~4 chain-like alkyl.
As the example of alkyl, can specifically enumerate：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth
Base, n-pentyl, isopentyl, neopentyl, n-hexyl.
The alkenyl that carbon atom number is 2~6 can be cyclic alkenyl radical or chain alkenyl.In addition, in alkenyl double bond number
Preferably 1.The preferred lower limiting value of carbon atom number is 3,4 in the alkenyl, and preferred upper limit value is 3,4,5,6.Preferably, it selects
Select the alkenyl that carbon atom number is 2~5.As the example of alkenyl, can specifically enumerate：Vinyl, allyl, isopropenyl, alkene
Butyl, alkene amyl.It is identical as alkenyl to the specific choice of alkynyl.
As the example of halogenated alkyl, can specifically enumerate：Trifluoromethyl (- CF3), 2- fluoro ethyls, pentafluoroethyl group, 2,2,
2- trifluoroethyls, pentafluoroethyl group, 3- fluorine n-propyl, 2- fluorine isopropyl, 3,3,3- trifluoros n-propyl, five fluorine of 2,2,3,3,3- positive third
Base, 1,1,1,3,3,3- hexafluoro isopropyls, 4- fluorine normal-butyl, 3- fluorine sec-butyl, 5- fluorine n-pentyl, 4- fluorine isopentyl；Above-mentioned
In specific example, F can be replaced by Cl and/or Br.
As a kind of improvement of the application nonaqueous electrolytic solution, as a kind of improvement of the application nonaqueous electrolytic solution, R1、R4Respectively
It is respectively selected from substituted or unsubstituted C from independent1~6Alkyl, substituted or unsubstituted phenyl；R2、R3Separate difference
Selected from halogen atom, substituted or unsubstituted C1~6Alkyl, and R2、R3In at least one substituent group be selected from substitution or it is unsubstituted
C1~6Alkyl.
As a kind of improvement of the application nonaqueous electrolytic solution, R1、R4It is separate be respectively selected from it is substituted or unsubstituted
C1~6Alkyl, substituted or unsubstituted phenyl；R2、R3It is separate to be respectively selected from halogen atom, substitution C1~6Alkyl, and R2、R3
In at least one substituent group be selected from substitution C1~6Alkyl.
As a kind of improvement of the application nonaqueous electrolytic solution, R1、R4It is separate be respectively selected from it is substituted or unsubstituted
C1~3Alkyl, substituted or unsubstituted phenyl；R2、R3It is separate to be respectively selected from halogen atom, substituted C1~3Alkyl, and
R2、R3In at least one substituent group be selected from substitution C1~3Alkyl.
As a kind of improvement of the application nonaqueous electrolytic solution, alkoxy ester chemical combination object in following compound at least one
Kind：
As a kind of improvement of the application nonaqueous electrolytic solution, alkoxy ester chemical combination object is further selected from：
As a kind of improvement of the application nonaqueous electrolytic solution, structural formula such as II institute of formula of methane-disulfonic acid methylene ester compounds
Show：
As a kind of improvement of the application nonaqueous electrolytic solution, methane-disulfonic acid methylene ester compounds are in nonaqueous electrolytic solution
Mass fraction is 0.05%~3%.It, cannot be in positive table when the content of methane-disulfonic acid methylene ester compounds is less than 0.05%
Face forms complete and effective CEI films, to not can effectively prevent the pair caused by the electronics transfer between electrolyte and electrode
Reaction；And when methane-disulfonic acid methylene ester compounds content is more than 3%, thicker CEI films can be formed in positive electrode surface, caused
Lithium ion mobility resistance increases, and is unfavorable for the positive interface stability of battery in cyclic process.
It is further preferred that mass fraction range of the methane-disulfonic acid methylene ester compounds in nonaqueous electrolytic solution is preferred
The upper limit is followed successively by 2.8%, 2.5%, 2.0%, 1.5%, 1.0%, preferred lower limit is followed successively by 0.08%, 0.1%, 0.3%,
0.5%, 0.6%.It is further preferred that mass fraction of the methane-disulfonic acid methylene ester compounds in nonaqueous electrolytic solution is
0.1%~2%.
As a kind of improvement of the application nonaqueous electrolytic solution, quality of the alkoxy ester type compound in nonaqueous electrolytic solution point
Number preferably 0.01%~10%.When the additive amount of alkoxy ester type compound in the electrolytic solution is less than 0.01%, it is impossible to have
Effect ground forms stable SEI films, and the cycle performance of battery is without improvement；And when the content of alkoxy ester type compound is higher than 10%
When, the viscosity and cathode impedance of electrolyte are increased, the migration of lithium ion is slowed down.
It is further preferred that the preferred upper limit of mass fraction range of the alkoxy ester type compound in nonaqueous electrolytic solution according to
Secondary is 9%, 8%, 7%, 6%, 5%, and preferred lower limit is followed successively by 0.08%, 0.1%, 0.3%, 0.5%, 0.6%.It is further excellent
Selection of land, mass fraction of the alkoxy ester type compound in nonaqueous electrolytic solution are 0.1%~5%.
As a kind of improvement of the application nonaqueous electrolytic solution, non-aqueous organic solvent is selected from carbon atom number and is 1~8 and contains
The compound of at least one ester group.
As a kind of improvement of the application nonaqueous electrolytic solution, non-aqueous organic solvent be selected from ethylene carbonate, propene carbonate,
Butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbonic acid first
Propyl ester, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate, butyric acid
At least one of ethyl ester.
As a kind of improvement of the application nonaqueous electrolytic solution, lithium salts is optionally from least one in organic lithium salt or inorganic lithium salt
Kind.
As a kind of improvement of the application nonaqueous electrolytic solution, in lithium salts containing in fluorine element, boron element, P elements at least
It is a kind of.
As a kind of improvement of the application nonaqueous electrolytic solution, 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) (being abbreviated as LiFSI), double grass
Sour lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4) in (being abbreviated as LiDFOB) at least
It is a kind of.
Present invention also provides a kind of lithium ion batteries comprising electrolyte, positive plate, negative plate, isolation film and packaging
Foil；The positive plate includes plus plate current-collecting body and the positive diaphragm that is coated on plus plate current-collecting body, and negative plate includes negative pole currect collecting
Body and the cathode membrane being coated on negative current collector；The electrolyte is the nonaqueous electrolytic solution described in any of the above-described paragraph.
As a kind of improvement of the application lithium ion battery, it is described anode diaphragm include positive electrode active materials, binder and
Conductive agent.
As a kind of improvement of the application lithium ion battery, the positive electrode active materials are optionally from cobalt acid lithium LiCoO2, lithium
At least one of nickel manganese cobalt ternary material, LiFePO 4, LiMn2O4 or cobalt acid lithium are mixed with lithium-nickel-manganese-cobalt ternary material
Close object.
As a kind of improvement of the application lithium ion battery, the cathode membrane include negative electrode active material, binder and
Conductive agent.
As a kind of improvement of the application lithium ion battery, the negative electrode active material is carbon material and/or silicon materials.
Compared with prior art, the present invention is by making methane-disulfonic acid methylene ester compounds and alkoxy ester type compound
For functional additive package, the discharge-rate, cycle performance and high-temperature storage performance of battery are significantly improved.
Examples 1 to 7
The preparation of electrolyte：In water content<In the argon gas atmosphere glove box of 10ppm, by ethylene carbonate (being abbreviated as EC),
Diethyl carbonate (being abbreviated as DEC), propene carbonate (being abbreviated as PC), ethyl propionate, fluorinated ethylene carbonate (being abbreviated as FEC)
According to 20:30:20:25:5 mass ratio after mixing, obtains nonaqueous solvents, then the lithium salts LiPF that will fully dry6Dissolving
In above-mentioned nonaqueous solvents, it is made into LiPF6The basic electrolyte of a concentration of 1mol/L.
Shown in table 1, methane-disulfonic acid methylene ester compounds and alkoxy ester chemical combination object are added in basic electrolyte.
Example as alkoxy ester chemical combination object：Tetra- fluoro- 2- methoxy propyls acid esters (as shown in Equation 1) of methyl 2,3,3,3-,
Tetra- fluoro- 2- ethoxy-cs acid esters (as shown in Equation 2) of ethyl 2,3,3,3-, tetra- fluoro- 2- benzyloxies propionic esters of phenyl 2,3,3,3-
(as shown in Equation 3).
The preparation of lithium ion battery：
1) preparation of positive plate：By positive active material cobalt acid lithium (molecular formula LiCoO2), conductive agent acetylene black, bonding
Agent polyvinylidene fluoride (being abbreviated as PVDF) is by weight 96:2:2 in suitable N-Methyl pyrrolidone (being abbreviated as NMP) solvent
In be thoroughly mixed, form it into uniform anode sizing agent；This slurry is coated on plus plate current-collecting body Al foils, dries, is cold
Pressure, obtains positive plate.
2) preparation of negative plate：Negative electrode active material graphite, conductive agent acetylene black, binder butadiene-styrene rubber (are abbreviated as
SBR), thickener sodium carboxymethylcellulose (being abbreviated as CMC) is according to weight ratio 95:2:2:1 in suitable deionized water solvent
It is thoroughly mixed, forms it into uniform negative electrode slurry；This slurry is coated on negative current collector Cu foils, drying, cold pressing,
Obtain negative plate.
3) isolation film：Using PE porous polymer films as isolation film.
4) preparation of lithium ion battery：Positive plate, isolation film, negative plate are folded in order, isolation film is made to be in positive and negative
Play the role of isolation between pole piece, then winding obtains naked battery core；Naked battery core is placed in outer packing foil, is prepared above-mentioned
Electrolyte be injected into it is dry after battery in, by processes such as Vacuum Package, standing, chemical conversion, shapings, that is, complete lithium-ion electric
The preparation in pond.
Comparative example 1~6
Basic electrolyte is prepared according to the method for embodiment 1, comparative example 1 is not added additive, is electrolysed in comparative example 2~6
Solution additive and respective additive amount are as shown in table 1.
Examples 1 to 7 and electrolysis additive in comparative example 1~6 and respective additive amount are as shown in table 1 in order to make this
Goal of the invention, technical solution and the technique effect of invention are more clear, and with reference to embodiments, are carried out to the present invention further detailed
It describes in detail bright.It should be understood that embodiment described in this specification is merely to the explanation present invention, is not intended to limit this hair
It is bright.
Examples 1 to 7 and electrolysis additive in comparative example 1~6 and respective additive amount refer to table 1.
Electrolysis additive combination in table 1, each comparative example and embodiment and additive amount
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, discharge-rate 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 4.4V again constant pressure to 0.05C, respectively with 0.5C,
1C, 2C, 3C, 5C, 7C, 10C discharge, and using the capacitance of 0.5C as benchmark (100%), calculate the capacity of different multiplying electric discharge.
Selected electrolyte and obtained relevant test data are referring to table 2 in each lithium ion battery.
2. discharge-rate test result (unit %) of table
| Group | 0.5C | 1C | 2C | 3C | 5C |
| Embodiment 1 | 100% | 94.90% | 92.30% | 89.30% | 68.30% |
| Embodiment 2 | 100% | 91.20% | 91.40% | 88.50% | 65.50% |
| Embodiment 3 | 100% | 90.40% | 88.30% | 85.90% | 56.90% |
| Embodiment 4 | 100% | 93.40% | 90.80% | 83.80% | 53.80% |
| Embodiment 5 | 100% | 91.50% | 88.70% | 78.00% | 48.00% |
| Embodiment 6 | 100% | 90.80% | 86.50% | 80.10% | 50.10% |
| Embodiment 7 | 100% | 88.80% | 86.50% | 73.10% | 47.10% |
| Comparative example 1 | 100% | 81.5% | 73.7% | 62.7% | 32.7% |
| Comparative example 2 | 100% | 86.1% | 78.5% | 69.8% | 46.8% |
| Comparative example 3 | 100% | 85.4% | 78.2% | 68.6% | 38.6% |
| Comparative example 4 | 100% | 86.5% | 82.9% | 73.9% | 41.0% |
| Comparative example 5 | 100% | 87.4% | 84.4% | 75.0% | 42.0% |
| Comparative example 6 | 100% | 80.5% | 69.7% | 57.7% | 28.7% |
It can be seen that compared with comparative example 1 in conjunction in Tables 1 and 2,5% be individually added into the electrolyte of comparative example 2~3
When 2,3,3,3- tetra- fluoro- 2- methoxy propyls acid esters of methyl or 1% methane-disulfonic acid methylene ester compounds, the electric discharge of lithium ion battery
Multiplying power slightly improves.It is fluoro- that the methyl 2,3,3,3- tetra- that mass fraction is 5% is added simultaneously in Examples 1 to 7, in electrolyte
When the methane-disulfonic acid methylene ester compounds that 2- methoxy propyls acid esters and mass fraction are 1%, the discharge capacity of battery significantly carries
It rises.However, it is more than 10% or the esterification of methane-disulfonic acid methylene to work as 2,3,3,3- tetra- fluoro- 2- methoxy propyls acid esters of methyl in electrolyte
When the content of conjunction object is more than 3%, not only the discharge capacity of battery does not improve, or even can deteriorate, the reason is that methyl 2,3,3,3-
Film thickness can be led into when four fluoro- 2- methoxy propyls acid esters and/or excessive methane-disulfonic acid methylene ester compounds, lithium ion conduction becomes
It obtains and adds 11% methyl 2,3,3,3-, tetra- fluoro- 2- methoxy propyls acid esters and 4% methane-disulfonic acid Asia in difficult especially electrolyte
The discharge capacity of the comparative example 6 of methyl compound, battery is far below other groups.
Test two, loop test
The lithium ion battery being prepared respectively is subjected to following tests：
At 25 DEG C, by lithium ion battery, with 1C constant-current charges to 4.4V, then constant voltage discharge to electric current is 0.05C, then
, according to above-mentioned condition into so many cycle discharged/discharged of places, divided at this time to recycle for the first time with 1C constant-current discharges to 3.0V
Be not calculated lithium ion battery recycle 50 times, 60 times, 200 times, 300 times and 500 times after capacity retention ratio, every group each 5
Battery, wherein the capacity retention ratio after cycle is calculated according to the following formula.In each lithium ion battery selected electrolyte with
And obtained relevant test data is referring to table 3.
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 3 for ring test.
Capacity retention ratio (%) after table 3, cycle
| Group | 50 times | 100 times | 200 times | 300 times | 500 times |
| Embodiment 1 | 97.90% | 95.70% | 93.90% | 91.30% | 88.30% |
| Embodiment 2 | 97.00% | 95.50% | 93.20% | 91.40% | 86.50% |
| Embodiment 3 | 97.40% | 95.30% | 93.40% | 90.30% | 86.90% |
| Embodiment 4 | 97.10% | 95.50% | 93.40% | 90.80% | 85.80% |
| Embodiment 5 | 96.40% | 94.30% | 92.50% | 88.70% | 84.00% |
| Embodiment 6 | 96.40% | 94.80% | 90.60% | 86.50% | 82.10% |
| Comparative example 1 | 95.3% | 91.5% | 83.5% | 73.7% | 62.7% |
| Comparative example 2 | 95.2% | 92.1% | 86.4% | 78.2% | 68.6% |
| Comparative example 3 | 95.0% | 92.2% | 86.6% | 78.5% | 67.8% |
| Comparative example 4 | 95.8% | 91.7% | 86.4% | 79.9% | 68.9% |
| Comparative example 5 | 95.8% | 92.5% | 88.4% | 84.4% | 75.0% |
| Comparative example 6 | 95.9% | 90.9% | 82.9% | 73.1% | 60.3% |
It can be seen that compared with comparative example 1 in conjunction in table 1 and table 3,5% be individually added into the electrolyte of comparative example 2~3
When 2,3,3,3- tetra- fluoro- 2- methoxy propyls acid esters of methyl or 1% methane-disulfonic acid methylene ester compounds, the cycle of lithium ion battery
Performance slightly improves.It is fluoro- that the methyl 2,3,3,3- tetra- that mass fraction is 5% is added simultaneously in Examples 1 to 6, in electrolyte
When the methane-disulfonic acid methylene ester compounds that 2- methoxy propyls acid esters and mass fraction are 1%, the cycle performance of battery significantly carries
It rises.However, it is more than 10% or the esterification of methane-disulfonic acid methylene to work as 2,3,3,3- tetra- fluoro- 2- methoxy propyls acid esters of methyl in electrolyte
When the content of conjunction object is more than 1%, not only the cycle performance of battery does not improve, or even can deteriorate, and is especially added in electrolyte
The comparative example 6 of 11% methyl 2,3,3,3- tetra- fluoro- 2- methoxy propyls acid esters and 4% methane-disulfonic acid methylene ester compounds, electricity
The cycle conservation rate in pond is far below other groups.
Test three, high temperature storage test
The lithium ion battery being prepared respectively is subjected to following tests：
With 0.5C electric currents constant-current charge to 4.4V at 25 DEG C, 4.4V constant-voltage charges to electric current are 0.025C, are at
Then battery is placed in 85 DEG C of high temperature furnace and is kept for 24 hours by 4.4V fully charged states, while being surveyed once per 4h heat；With 100%
SOC battery cores thickness records the thickness data of battery core as benchmark (0%).
The results are shown in Table 4 for high temperature storage test.
Made from table 4, each comparative example and embodiment 25 DEG C cycle after battery hot tank test after result
As can be seen from Table 4,2,3,3,3- tetra- fluoro- 2- methoxy propyls acid esters of methyl and methane-disulfonic acid methylene ester is added
Compound can reduce the thickness increase of battery during high temperature storage.When tetra- fluoro- 2- methoxy propyls acid esters of methyl 2,3,3,3-
Content when being higher than 10%, high temperature causes thicker SEI to dissolve rupture, causes lithium metal in battery cathode to be precipitated, with electrolyte
Reduction reaction aerogenesis occurs and deteriorates battery high-temperature storage performance.In contrast, the esterification of methane-disulfonic acid methylene is added in electrolyte
The expansion character of high temperature storage battery can be effectively improved by closing object.Therefore, methane-disulfonic acid methylene ester compounds and methyl 2,3,
3,3- tetra- fluoro- 2- methoxy propyls acid esters are arranged in pairs or groups in use, battery high-temperature can be significantly improved as electrolysis additive and are deposited simultaneously
Store up performance.
By all of above description it is found that the alkane that the present invention is less than 10% by the way that mass fraction is added simultaneously in the electrolytic solution
Oxygroup esters and mass fraction are less than 3% methane-disulfonic acid methylene ester compounds, can significantly improve lithium ion battery
Discharge-rate, service life, high-temperature storage performance.
Embodiment 8~14
Electrolyte and lithium ion battery are prepared according to the method for embodiment 1, difference lies in：The formula of electrolyte such as 5 institute of table
Show：
The electrolysis additive formula of table 5, embodiment 8~14
The discharge-rate of the lithium ion battery that embodiment 8~14 is prepared, capacity retention ratio, high-temperature storage performance with
Upper embodiment is close, and details are not described herein.
According to the disclosure and teachings of the above specification, the application those skilled in the art can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the application is not limited to specific implementation mode disclosed and described above, to this
Some modifications and changes of application should also be as falling into the protection domain of claims hereof.In addition, although this specification
In used some specific terms, these terms are merely for convenience of description, not to the application constitute any restrictions.
Claims (10)
1. a kind of nonaqueous electrolytic solution, including non-aqueous organic solvent, lithium salts and additive, it is characterised in that：The additive contains
Methane-disulfonic acid methylene ester and alkoxy ester type compound, the structural formula of the alkoxy ester type compound is as shown in formula I：
Wherein, R1、R4It is separate to be respectively selected from substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted C6~26Aryl；
R2、R3It is separate to be respectively selected from hydrogen atom, halogen atom, substituted or unsubstituted C1~6Alkyl, substitution or unsubstituted
C1~6Alkylene, and R2、R3In at least one substituent group be selected from halogen substitution C1~6Alkyl；
Substituent group is selected from halogen, and the halogen is selected from F or Cl；
Mass percentage content of the methane-disulfonic acid methylene ester in nonaqueous electrolytic solution is 0.05%~3%, the alcoxyl
Mass percentage content of the base ester type compound in nonaqueous electrolytic solution is 0.01%~10%.
2. nonaqueous electrolytic solution according to claim 1, which is characterized in that R1、R4It is separate be respectively selected from substitution or not
Substituted C1~6Alkyl, substituted or unsubstituted phenyl；
R2、R3It is separate to be respectively selected from halogen atom, substituted or unsubstituted C1~6Alkyl, and R2、R3In at least one
Substituent group is selected from the C of halogen substitution1~6Alkyl.
3. nonaqueous electrolytic solution according to claim 1, which is characterized in that the alkoxy ester type compound is selected from followingization
Close at least one of object：
4. nonaqueous electrolytic solution according to claim 1, which is characterized in that the methane-disulfonic acid methylene ester is in non-aqueous solution electrolysis
Mass percentage content in liquid is 0.1%~2%.
5. nonaqueous electrolytic solution according to claim 1, which is characterized in that the alkoxy ester type compound is in non-aqueous solution electrolysis
Mass percentage content in liquid is 0.1%~5%.
6. nonaqueous electrolytic solution according to claim 1, which is characterized in that the non-aqueous organic solvent is selected from carbon atom number
1~8 and containing at least one ester group compound.
7. nonaqueous electrolytic solution according to claim 6, which is characterized in that the non-aqueous organic solvent is selected from ethylene carbonate
Ester, propene carbonate, butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid
Dipropyl, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate,
At least one of propyl propionate, ethyl butyrate.
8. nonaqueous electrolytic solution according to claim 1, which is characterized in that the lithium salts is optionally from organic lithium salt or inorganic lithium
At least one of salt.
9. nonaqueous electrolytic solution according to claim 8, which is characterized in that the lithium salts is selected from lithium hexafluoro phosphate, double trifluoros
At least one of sulfonyl methane imine lithium, bis- (fluorine sulphonyl) imine lithiums, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium.
10. a kind of lithium ion battery comprising electrolyte, positive plate, negative plate, 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 plate include negative current collector and are coated on cathode collection
Cathode membrane on fluid；It is characterized in that：The electrolyte nonaqueous electrolytic solution as claimed in any one of claims 1 to 9.
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| CN111384442B (en) * | 2018-12-29 | 2023-09-12 | 浙江省化工研究院有限公司 | Positive electrode film forming additive for battery electrolyte, electrolyte using additive and lithium ion battery |
| CN111755747B (en) * | 2019-03-29 | 2021-09-21 | 比亚迪股份有限公司 | Non-aqueous electrolyte, battery containing non-aqueous electrolyte and vehicle containing battery |
| CN112216865A (en) * | 2019-07-12 | 2021-01-12 | 东莞市杉杉电池材料有限公司 | Lithium metal battery electrolyte and lithium metal battery |
| CN116646526B (en) * | 2023-07-25 | 2023-10-20 | 中国华能集团清洁能源技术研究院有限公司 | Positive electrode interface film of sodium ion battery, preparation method of positive electrode interface film and sodium ion battery |
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| US9130244B2 (en) * | 2009-09-15 | 2015-09-08 | Ube Industries, Ltd. | Nonaqueous electrolyte solution and electrochemical element using same |
| CN105140564B (en) * | 2015-07-28 | 2017-11-24 | 东莞市凯欣电池材料有限公司 | A kind of high voltage tertiary cathode material system lithium-ion battery electrolytes |
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