CN110085914A - A kind of Soft Roll high-voltage lithium-ion battery electrolyte and a kind of lithium ion battery - Google Patents
A kind of Soft Roll high-voltage lithium-ion battery electrolyte and a kind of lithium ion battery Download PDFInfo
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- CN110085914A CN110085914A CN201910482245.5A CN201910482245A CN110085914A CN 110085914 A CN110085914 A CN 110085914A CN 201910482245 A CN201910482245 A CN 201910482245A CN 110085914 A CN110085914 A CN 110085914A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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Abstract
The present invention provides a kind of Soft Roll high-voltage lithium-ion battery electrolyte and a kind of lithium ion battery, the electrolyte includes the first additive and Second addition, first additive is compound shown in compound and/or Formula II shown in Formulas I, the Second addition be formula III, in compound shown in formula IV or Formula V any one or at least two combination.The electrolyte oxygenolysis voltage with higher, operation window temperature range is wide, and security performance is high, and good with wettability that electrode material is shown in.
Description
Technical field
The invention belongs to field of lithium ion battery, it is related to a kind of lithium-ion battery electrolytes more particularly to a kind of Soft Roll is high
Voltage lithium-ion battery electrolytes and a kind of lithium ion battery.
Background technique
Continuous with portable electrical equipment, charge power supply and mobile device is popularized, and consumer is to many performances of battery
Such as output voltage, energy density, quick charge and discharge, cycle life, temperature applicable range, security performance propose higher want
It asks.Fluorine has very strong electronegativity and low pole, and fluoro additive has low melting point, high-flash, high oxidation decomposition voltage etc. excellent
Point.Wetability between fluoro additive and electrode material is preferable, in high-voltage electrolyte, high security electrolyte, wide temperature
It finds broad application in window electrolyte and other specific function electrolyte.
Fluorine atom has very strong electronegativity and low pole, and fluorine replaces four class additive oxygenolysis voltages after hydrogen to obtain
To raising, fusing point is reduced, and flash-point improves, and is conducive to the low temperature and security performance that improve electrolyte.Fluorinated additive is by fluorine
The sucting electronic effect raising central atom of atom obtains electronic capability, makes additive under higher potential condition in cathode interface
Simultaneously effective passivated electrodes surface is restored, is equally increased using the cycle efficieny and security performance of electrolyte, acquisition meets height
The electrolyte of voltage 4.45V or more.
The effect in the lithium-ion battery electrolytes that exploitation has specific function of fluoro additive is obvious.Fluorine is No. nine member
Element, electron orbit outermost layer have seven electronics, have very strong electronegativity and low pole, and fluoro can make additive freezing point
It reduces, flash-point raising, inoxidizability raising, and helps to promote the wetability between electrolyte and electrode.Therefore, fluoro adds
Add the use of agent in the electrolytic solution that can effectively improve the cryogenic property of electrolyte, oxidation resistent susceptibility, flame retardant property and to electrode
Wetability, and then the electrolyte with specific function is obtained, such as high-voltage electrolyte, wide temperature window electrolyte and other types
Electrolyte.
Frontier orbital theory is one of the tool for developing high-voltage electrolyte, and frontier orbital theory is thought: substance is reacting
In the process, what is interacted is molecular orbit, and what is preferentially worked is exactly frontier orbit.Molecule highest occupied molecular orbital energy
Measure (HOMO) it is higher, the electronics in track is more unstable, easier lose and be oxidized；On the contrary, molecule is minimum not to occupy track
Energy (LUMO) is lower, is more easy to get electronics and is reduced.Molecular dipole moment determines the polarity of molecule, and molecular dipole moment is got over
Greatly, molecular polarity is bigger, and dielectric constant is bigger, lithium salts also easier dissociation wherein.
Summary of the invention
To solve the technical problems existing in the prior art, the present invention provides a kind of Soft Roll high-voltage lithium ion batteries electrolysis
Liquid and a kind of lithium ion battery, the electrolyte oxygenolysis voltage with higher, operation window temperature range is wide, safety
Can be high, and the wettability between electrode material is good.
In order to achieve the above object, the invention adopts the following technical scheme:
It is an object of the present invention to provide a kind of Soft Roll high-voltage lithium-ion battery electrolyte, the electrolyte includes the
One additive and Second addition, first additive is compound shown in compound shown in Formulas I and/or Formula II, described
Second addition be formula III, in compound shown in formula IV or Formula V any one or at least two combination；
Wherein, R1、R2、R3、R4And R5It is separately C1~C10 alkyl substituted or unsubstituted, the substituent group is F
And/or trifluoromethyl.
In the present invention, the high-voltage lithium ion batteries are the lithium ion battery of voltage 4.45V or more.
It is that fluorine atom and alkyl replace from the first additive in the structure of compound shown in the Formulas I and Formula II for including
Ethylene glycol acetal, F substituent group has very strong electron-withdrawing ability, and under higher current potential, compound shown in Formulas I and Formula II can
Reduction decomposition reaction occurs.Known by EDS (energy dispersive spectroscopy) analysis, after adding the first additive, graphite electrode surface face
The main component member of SEI film is known as C, O, F, decomposition product of the F therein from compound shown in Formulas I and/or Formula II.
O and Li in compound shown in Formulas I and Formula II on carbonyl+There is strong coordination, obtains also primary after an electronics
At radical anion intermediate, intermediate has very high reactivity, and dimerization reaction can occur or send out with other intermediates
Raw reaction, generates other products, under higher reduction potential, the fluorine-containing product of generation first occupies the active sites of graphite electrode surface
Point can effectively inhibit the decomposition compared with electrolyte solvent under low potential.
As currently preferred technical solution, the electrolyte includes lithium salts, organic solvent, the first additive and second
Additive.
As currently preferred technical solution, first additive accounts for the 0.5~12% of the electrolyte gross mass,
Such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or 11%, it is not limited to cited numerical value,
Other unlisted numerical value are equally applicable in the numberical range, and preferably 3~8%, further preferably 5%.
Preferably, it is described second addition account for the 0.5~3% of the electrolyte gross mass, such as 0.6%, 0.8%, 1%,
1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5% or 2.8% etc., it is not limited to cited numerical value, the numerical value model
Other unlisted numerical value are equally applicable in enclosing, and preferably 1~2.5%, further preferably 2%.
As currently preferred technical solution, the organic solvent accounts for the 65~85% of the electrolyte gross mass, such as
66%, 68%, 70%, 72%, 75%, 78%, 80% or 82% etc., it is not limited to cited numerical value, the numerical value model
Other unlisted numerical value are equally applicable in enclosing.
As currently preferred technical solution, the organic solvent includes ethylene carbonate, outside propene carbonate, is also wrapped
Include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, propyl propionate, ethyl propionate, propyl acetate, butyric acid
Ethyl ester, butyl butyrate, Trifluoroacetic Acid Ethyl Ester, tri- fluoro methyl ethyl carbonate of 2,2,2-, tri- fluoro diethyl carbonate of 2,2,2- or 2,
One of tri- fluoro ethyl propyl carbonic acid ester of 2,2- or multiple combinations.The organic solvent removes ethylene carbonate or propene carbonate
It outside, further include that the combination is typical but non-limiting example has: the combination of dimethyl carbonate and diethyl carbonate, diethyl carbonate
The combination of combination, gamma-butyrolacton and propyl propionate, the combination of ethyl propionate and propyl acetate, propionic acid second with methyl ethyl carbonate
The combination of ester and propyl acetate, the combination of propyl acetate and ethyl butyrate, ethyl butyrate and butyl butyrate combination, butyl butyrate
Combination, tri- fluoro of 2,2,2- of combination, Trifluoroacetic Acid Ethyl Ester and tri- fluoro methyl ethyl carbonate of 2,2,2- with Trifluoroacetic Acid Ethyl Ester
Combination, tri- fluoro diethyl carbonate of 2,2,2- and tri- fluoro of 2,2,2- of tri- fluoro diethyl carbonate of methyl ethyl carbonate and 2,2,2-
The combined combination etc. of the tri- fluoro diethyl carbonate of combination, ethyl butyrate and 2,2,2- of ethyl propyl carbonic acid ester.
As currently preferred technical solution, the lithium salts accounts for the 8.5~17.5% of the electrolyte gross mass, such as
9%, 9.5%, 10%, 10.5%, 11%, 12%, 13%, 14%, 15%, 15.5%, 16%, 16.5% or 17% etc., but
It is not limited in cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
As currently preferred technical solution, the lithium salts is mainly lithium hexafluoro phosphate, further includes difluorophosphate, nitre
It is sour lithium, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, difluoro oxalate lithium phosphate, tetrafluoro oxalic acid lithium phosphate, double
It is any one in lithium trifluoromethanesulp,onylimide, difluoro lithium sulfimide, difluoro dimalonic acid lithium phosphate or lithium perchlorate etc.
Kind or at least two combination, combination typical case but non-limiting example has: the combination of difluorophosphate and lithium nitrate, tetrafluoro
The combination of lithium borate and di-oxalate lithium borate, the combination of di-oxalate lithium borate and difluorine oxalic acid boracic acid lithium, difluorine oxalic acid boracic acid lithium
The combination of combination, difluoro oxalate lithium phosphate and tetrafluoro oxalic acid lithium phosphate with difluoro oxalate lithium phosphate, tetrafluoro oxalic acid lithium phosphate and
The combination of bis trifluoromethyl sulfimide lithium, the combination of bis trifluoromethyl sulfimide lithium and difluoro lithium sulfimide, double fluorine
For the combination of sulfimide lithium and difluoro dimalonic acid lithium phosphate, difluoro oxalate lithium phosphate and bis trifluoromethyl sulfimide lithium
Combination etc..
As currently preferred technical solution, the electrolyte includes auxiliary additive.
Preferably, the auxiliary additive includes calgon, tricresyl phosphate alkynes propyl ester, vinylene carbonate, 1,3- third
Sultone, fluorinated ethylene carbonate, difluoroethylene carbonate, vinylethylene carbonate, 1,3- propene sultone,
Isosorbide-5-Nitrae-butyl sultone, 1,1,2,2- tetra- fluoro ethyl -2,2, the double propionitrile ethers of 3,3- tetrafluoro propyl ethers, ethylene glycol, three (2,2,2-
Trifluoroethyl) it is phosphite ester, succinonitrile, adiponitrile, three nitrile of 1,3,6- hexane, citric anhydride, fluorobenzene, 2- fluorine biphenyl, borontrifluoride
Boron tetrahydrofuran, three (trimethyl silane) phosphates, three (trimethyl silane) borates, five fluorine (phenoxy group) ring, three phosphonitrile, lemon
In health acid anhydrides or methane-disulfonic acid methylene ester any one or at least two combination.
The second purpose of the present invention is to provide a kind of lithium ion battery, the battery include anode, cathode, be placed in it is described just
Diaphragm and electrolyte between pole and cathode, the electrolyte are electrolyte described in any of the above-described kind.
As currently preferred technical solution, the active material of the anode is LiNixCoyMnzM1-x-y-zO2Or
LiNixCoyAlzM1-x-y-zO2, wherein it is any one in M Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti
Kind, and 0≤y≤1,0≤x < 1,0≤z≤1, x+y+z≤1, the active material of the cathode be natural graphite, artificial graphite,
Any one in composite graphite or silicon-carbon cathode material.
Compared with prior art, the present invention at least has the advantages that
(1) present invention provides a kind of Soft Roll high-voltage lithium-ion battery electrolyte, and lithium ion can be improved in the electrolyte
The normal-temperature circulating performance of battery, 25 DEG C 0.5C charge and discharge 600 weeks, capacity retention ratio is up to 89% or more；
(2) present invention provides a kind of Soft Roll high-voltage lithium-ion battery electrolyte, and lithium ion can be improved in the electrolyte
The high temperature cyclic performance of battery, 45 DEG C 0.5C charge and discharge 500 weeks, capacity retention ratio is up to 85% or more；
(3) present invention provides a kind of Soft Roll high-voltage lithium-ion battery electrolyte, and lithium ion can be improved in the electrolyte
The high-temperature storage performance of battery；
(4) present invention provides a kind of Soft Roll high-voltage lithium-ion battery electrolyte, and lithium ion can be improved in the electrolyte
The low temperature performance of battery.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment provides a kind of Soft Roll lithium ion silicon-carbon battery, preparation method is as follows:
(1) anode preparation: by high-voltage anode active material high voltage 4.45V cobalt acid lithium (LiCoO2) (being purchased from China fir China fir),
CNTs (carbon nanotube), conductive carbon and PVDF (Kynoar) are uniformly mixed according to mass ratio 98.2:0.5:0.3:1.0, so
After be dispersed in n-methyl-2-pyrrolidone, obtain anode sizing agent；Anode sizing agent is uniformly coated on to the two sides of aluminium foil, is passed through
Roll, cut after obtain positive plate, it is finally stand-by after overbaking and vacuum drying.
(2) prepared by cathode: by G49 negative electrode material (being purchased from Jiangxi purple occasion), conductive carbon, CMC (carboxymethyl cellulose) and SBR
It is uniformly mixed according to mass ratio 97.0:0.4:1.2:1.4, is then dispersed in deionized water, obtains negative electrode slurry；Cathode is starched
Material, which is divided equally, is coated on the two sides of copper foil, and negative electrode tab is obtained after rolling, cutting, finally after overbaking and vacuum drying to
With.
(3) electrolyte quota: in the glove box (O for being full of nitrogen2< 2ppm, H2O < 3ppm) in, by ethylene carbonate, carbon
Acid propylene ester, ethyl propionate, propyl propionate, diethyl carbonate are uniformly mixed according to mass ratio 2:1:1:4:2, are made organic molten
Agent；Then the organic solvent for accounting for electrolyte gross mass 69% is taken, FEC based on electrolyte gross mass 1%, 3% are added thereto
PS, 1% tetra- fluoro ethyl -2,2,3,3- tetrafluoro propyl ether of 1,1,2,2-, the double propionitrile ether of 1% ethylene glycol, 2% adiponitrile, 1%
1,3,6- hexane, three nitrile, 0.5% DTD auxiliary additive and 5% the first additive and 2% Second addition, obtain
To mixed solution；Lithium hexafluoro phosphate, difluorine oxalic acid boracic acid lithium, difluoro oxalate lithium phosphate and double are slowly added into mixed solution again
The mixture of fluoro sulfimide lithium is configured to the lithium salt solution of 1.25mol/L, and wherein lithium hexafluoro phosphate accounts for electrolyte gross mass
13.5%, be made electrolyte after mixing.
(4) prepared by lithium ion battery: positive plate, coated ceramic diaphragm (being purchased from Asahi Chemical Industry), negative electrode tab are arranged in order
Coiling obtains naked battery core, through aluminum plastic film encapsulation, again toast, fluid injection, standing, fixture chemical conversion, two envelopes, volume test, complete lithium from
The preparation of sub- soft-package battery.
Wherein, the first additive is compound shown in Formulas I, R1For-C2H5, Second addition is compound shown in formula III,
R3For-C2H5。
Embodiment 2
The present embodiment provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method that uses
1。
In the preparation of electrolyte, other than Second addition uses compound shown in formula IV, other conditions with embodiment 1
It is identical.Wherein, the R of compound shown in formula IV4For-CH3。
Embodiment 3
The present embodiment provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method that uses
1。
In the preparation of electrolyte, other than Second addition uses compound shown in Formula V, other conditions with embodiment 1
It is identical.Wherein, the R of compound shown in Formula V5For trifluoromethyl.
Embodiment 4
The present embodiment provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method that uses
1。
In the preparation of electrolyte, other than the first additive uses compound shown in Formula II, other conditions with embodiment 1
It is identical.Wherein, the R of compound shown in Formula II2For-CH3。
Embodiment 5
The present embodiment provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method that uses
1。
In the preparation of electrolyte, other than Second addition uses compound shown in formula IV, other conditions with embodiment 4
It is identical.Wherein, the R of compound shown in formula IV4For-CH3。
Embodiment 6
The present embodiment provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method that uses
1。
In the preparation of electrolyte, other than Second addition uses compound shown in Formula V, other conditions with embodiment 4
It is identical.Wherein, the R of compound shown in Formula V5For trifluoromethyl.
Embodiment 7
The present embodiment provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method that uses
1。
In the preparation of electrolyte, in addition to organic solvent accounts for the 67% of electrolysis gross mass, the first additive accounts for the total matter of electrolyte
Outside the 7% of amount, other conditions are same as Example 1.
Embodiment 8
The present embodiment provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method that uses
1。
In the preparation of electrolyte, in addition to organic solvent accounts for the 72.5% of electrolysis gross mass, it is total that the first additive accounts for electrolyte
The 0.5% of quality, Second addition account for outside the 3% of electrolyte gross mass, and other conditions are same as Example 1.
Embodiment 9
The present embodiment provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method that uses
1。
In the preparation of electrolyte, in addition to organic solvent accounts for the 65% of electrolysis gross mass, the first additive accounts for the total matter of electrolyte
The 10.5% of amount, Second addition accounts for outside the 0.5% of electrolyte gross mass, and other conditions are same as Example 1.
Comparative example 1
This comparative example provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method used
1。
In the preparation of electrolyte, in addition to the first additive accounts for the 7% of electrolyte gross mass, do not add outside Second addition,
Other conditions are same as Example 1.
Comparative example 2
This comparative example provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method used
1。
In the preparation of electrolyte, in addition to organic solvent accounts for the 74% of electrolysis gross mass, the first additive is not added, second adds
Agent is added to account for outside the 2% of electrolyte gross mass, other conditions are same as Example 1.
Comparative example 3
This comparative example provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method used
1。
In the preparation of electrolyte, in addition to organic solvent accounts for the 76% of electrolysis gross mass, the first additive and the are not added
Outside two additives, other conditions are same as Example 1.
Comparative example 4
This comparative example provides a kind of soft bag lithium ionic cell, the same embodiment of anode, cathode and its assembly method used
1。
In the preparation of electrolyte, in addition to organic solvent accounts for the 66% of electrolysis gross mass, the first additive accounts for the total matter of electrolyte
The 5% of amount, Second addition accounts for outside the 5% of electrolyte gross mass, and other conditions are same as Example 1.
The correlated performance of the lithium ion battery of testing example 1-9 and comparative example 1-4 preparation respectively, including normal temperature circulation
Energy, high temperature circulation, high-temperature storage thickness swelling, low-temperature circulating analysis lithium observation, the specific test method is as follows:
(1) normal-temperature circulating performance is tested: at 25 DEG C, by the 0.5C constant-current constant-voltage charging to 4.45V of the battery after chemical conversion
(cut-off current 0.01C) calculates the conservation rate of 600 weeks circulation volumes of charge/discharge then with 0.5C constant-current discharge to 3.0V,
Its calculation formula is as follows:
Circulation 600 weeks capacity retention ratio (%)=600 week cyclic discharge capacity/1st time cyclic discharge capacity ×
100%.
(2) high temperature cyclic performance is tested: at 45 DEG C, by the 0.5C constant-current constant-voltage charging to 4.45V of the battery after chemical conversion
(cut-off current 0.01C) calculates the conservation rate of 500 weeks circulation volumes of charge/discharge then with 0.5C constant-current discharge to 3.0V,
Its calculation formula is as follows:
Circulation 500 weeks capacity retention ratio (%)=500 week cyclic discharge capacity/1st time cyclic discharge capacity ×
100%.
(3) high-temperature storage performance is tested: battery testing its thickness after chemical conversion is filled at 25 DEG C with the constant current constant voltage of 0.5C
Electricity to 4.45V (cut-off current 0.01C), be placed on 85 DEG C of preservation 12H of high temperature, after high temperature storage, surveyed in oven
The thickness of battery core or battery is measured, the increment rate of cell thickness before and after high temperature storage is calculated, calculation formula is as follows:
Cell thickness before cell thickness increment rate (%)=(cell thickness before cell thickness-high temperature after high temperature)/high temperature ×
100%.
(4) negative electrode tab analysis lithium observation: with 0.3C constant-current constant-voltage charging to 4.45V, (cut-off current is under -5 DEG C of environment
0.01C), then with 0.3C constant-current discharge to 3.0V, charge and discharge cycles 10 weeks, dissect battery according to this, and whether observation negative electrode tab is analysed
Lithium.
(5) -20 DEG C of electric discharge ratios: with 0.5C constant-current constant-voltage charging to 4.45V, (cut-off current is under 25 DEG C of environment
0.01C), battery is placed on 4H under -20 DEG C of environment, then with 0.2C constant-current discharge to 3.0V, records discharge capacity, calculates public
Formula is as follows:
Room temperature capacity × 100% of -20 DEG C of electric discharge ratio (%)=- 20 DEG C of discharge capacities/initial
The percentage (wt%) that additive accounts for electrolyte gross mass is as shown in table 1.
Table 1
Can be seen that the first additive and Second addition from the test result of table 1 has circulation and low temperature charge and discharge
It helps, wherein the first additive is more advantageous to the circularly enhancing of battery, Second addition promotes low temperature discharge bigger.
Second addition is the substituent of cyclic carboxylic esters, has Acclimation temperature window more broader than cyclic carboxylic esters, with electricity
Pole piece wetability is improved, and after fluoro, oxidation resistance is promoted cyclic carboxylic esters, is more adapted to than cyclic carboxylic esters
In high-voltage battery.
From embodiment and comparative example it can be seen that, compound shown in compound or Formula II shown in Formulas I and formula III, formula IV or
Compound shown in Formula V is combined use by a certain percentage respectively, and relevant test data is essentially identical, and is better than any one of them
The exclusive use effect of additive.
It can see and remove from comparative example 3 and embodiment 1, the electrolyte of these two types of additives, the circulation of battery, height is not added
Cryogenic property decreases, and battery electricity dismantling full at low temperature, negative electrode tab analyses lithium.
The ratio of embodiment 7,9 and embodiment 1, which is haggled over, can see, and increase the additional amount of the first additive, the circulation of battery
There is promotion, but high temperature circulation, low temperature discharge and high temperature storage do not continue to lift up.
The comparison of comparative example 4, embodiment 8 and embodiment 1 can be seen that the additional amount for increasing Second addition, but super
The 2% of electrolyte gross mass is crossed, the high temperature circulation and high temperature storage of battery are in a slight decrease, and low temperature discharge is promoted.
In summary embodiment and comparative example, the first additive and Second addition are respectively by accounting for electrolyte gross mass
5% and 2% combination does use and is made into electrolyte, and every test data comprehensive performance of battery is optimal.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of Soft Roll high-voltage lithium-ion battery electrolyte, which is characterized in that the electrolyte include the first additive and
Second addition, first additive are compound shown in compound shown in Formulas I and/or Formula II, and the Second addition is
In compound shown in formula III, formula IV or Formula V any one or at least two combination；
Wherein, R1、R2、R3、R4And R5Separately be C1~C10 alkyl substituted or unsubstituted, the substituent group be F and/or
Trifluoromethyl.
2. electrolyte according to claim 1, which is characterized in that the electrolyte includes lithium salts, organic solvent, first adds
Add agent and Second addition.
3. electrolyte according to claim 1 or 2, which is characterized in that first additive accounts for the total matter of the electrolyte
The 0.5~12% of amount, preferably 3~8%, further preferably 5%；
Preferably, second addition accounts for the 0.5~3%, preferably 1~2.5% of the electrolyte gross mass, further preferably
It is 2%.
4. electrolyte according to claim 1-3, which is characterized in that it is total that the organic solvent accounts for the electrolyte
The 65~85% of quality.
5. electrolyte according to claim 1-4, which is characterized in that the organic solvent includes ethylene carbonate
Ester, propene carbonate and dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, propyl propionate, propionic acid second
Ester, propyl acetate, ethyl butyrate, butyl butyrate, Trifluoroacetic Acid Ethyl Ester, tri- fluoro methyl ethyl carbonate of 2,2,2-, 2,2,2- trifluoro
For in tri- fluoro ethyl propyl carbonic acid ester of diethyl carbonate or 2,2,2- any one or at least two combination.
6. electrolyte according to claim 1-5, which is characterized in that the lithium salts accounts for the electrolyte gross mass
8.5~17.5%.
7. electrolyte according to claim 1-6, which is characterized in that the lithium salts include lithium hexafluoro phosphate and
Difluorophosphate, lithium nitrate, hexafluorophosphoric acid caesium, LiBF4, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, difluoro oxalate
Lithium phosphate, tetrafluoro oxalic acid lithium phosphate, bis trifluoromethyl sulfimide lithium, difluoro lithium sulfimide, difluoro dimalonic acid phosphoric acid
In lithium or lithium perchlorate etc. any one or at least two combination.
8. electrolyte according to claim 1-7, which is characterized in that the electrolyte includes auxiliary additive；
Preferably, the auxiliary additive includes calgon, tricresyl phosphate alkynes propyl ester, vinylene carbonate, 1,3- propane sulphur
Acid lactone, fluorinated ethylene carbonate, difluoroethylene carbonate, vinylethylene carbonate, 1,3- propene sultone, Isosorbide-5-Nitrae-
The double propionitrile ethers of butyl sultone, tetra- fluoro ethyl -2,2,3,3- tetrafluoro propyl ether of 1,1,2,2-, ethylene glycol, three (2,2,2- trifluoros
Ethyl) phosphite ester, succinonitrile, adiponitrile, three nitrile of 1,3,6- hexane, citric anhydride, fluorobenzene, 2- fluorine biphenyl, boron trifluoride four
Hydrogen furans, three (trimethyl silane) phosphates, three (trimethyl silane) borates, five fluorine (phenoxy group) ring, three phosphonitrile, citraconic acid
In acid anhydride or methane-disulfonic acid methylene ester any one or at least two combination.
9. a kind of soft bag lithium ionic cell, which is characterized in that the battery includes anode, cathode, is placed in the anode and cathode
Between diaphragm and electrolyte, the electrolyte be the described in any item electrolyte of claim 1-8.
10. lithium ion battery according to claim 9, which is characterized in that the active material of the anode is
LiNixCoyMnzM1-x-y-zO2Or LiNixCoyAlzM1-x-y-zO2, wherein M Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga,
Any one in Cr, Sr, V or Ti, and 0≤y≤1,0≤x < 1,0≤z≤1, x+y+z≤1, the active material of the cathode
For any one in natural graphite, artificial graphite, composite graphite or silicon-carbon cathode material.
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