CN108649265A - Electrolysis additive, lithium battery electrolytes and lithium battery - Google Patents
Electrolysis additive, lithium battery electrolytes and lithium battery Download PDFInfo
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- CN108649265A CN108649265A CN201810442760.6A CN201810442760A CN108649265A CN 108649265 A CN108649265 A CN 108649265A CN 201810442760 A CN201810442760 A CN 201810442760A CN 108649265 A CN108649265 A CN 108649265A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of electrolysis additive, lithium battery electrolytes and lithium batteries, belong to technical field of lithium batteries.Additive includes at least one of compound shown in formula I：Wherein, R1、R2、R3It is selected from alkenyl, aromatic radical, carbon atom number C1~C13Alkyl, carbon atom number C1~C13Halogenated alkyl in one kind.The electrolysis additive of the present invention has higher oxidisability compared with organic solvent; electrochemical oxidation can preferentially occur in positive electrode surface; SEI protective films are formed in positive electrode surface; to effectively inhibit the organic solvent in electrolyte that oxygenolysis and the destruction to cathode material structure occur in cyclic process; widen the electrochemical window of electrolyte; the operating voltage range of battery is expanded, cyclical stability of the battery under high pressure (such as 4.5~5V) is especially improved.
Description
Technical field
The invention belongs to technical field of lithium batteries, be related to a kind of electrolysis additive and comprising its lithium battery electrolytes and
Lithium battery.
Background technology
With being growing for New-energy electric vehicle market, the lithium ion battery as major impetus source, which is faced with, to be chosen
War：The energy density for improving battery, increases the course continuation mileage of electric vehicle.Improve the operating voltage and positive and negative pole material of battery
Specific capacity is to promote the effective way of lithium ion battery energy density.
Pursue the important development direction that higher energy density is lithium ion battery, but high energy density lithium ion
One bottleneck of battery development is how to propose a kind of high pressure that with high energy lithium ion cell electrode material can be matched
Electrolyte.Currently, the voltage regime of conventional carbonic ester electrolyte is mainly based on 4.2V, for the positive material of high-energy density
Material, it would be desirable to be able to which the electrolyte of resistance to higher voltage system has foot for solvent, lithium salts and the positive interface in high-voltage electrolyte
Enough electrochemical stabilities.
At present by commercialization electrolyte electrochemical window limited, use commercialization positive electrode current potential all in
4.3V is hereinafter, such as LiFePO4 (LiFePO4), cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4) etc..And high-voltage positive electrode material
LiCoPO4(4.8V)、LiNi0.5Mn1.5O4(4.7V), rich lithium material and high pressure ternary material etc. fail in actual production so far
It is more than that violent oxygenolysis will occur is anti-by 4.5V to be to be commercialized electrolyte at present in cell voltage using, maximum reason
It answers, makes battery that can not be worked normally under stopping potential.Such as LiNi0.5Mn1.5O4Metal ion can be dissolved out under high pressure,
Material structure is destroyed, capacity attenuation is caused, therefore develops wide electrochemical window, the high-pressure electrolysis of electrode interface protective layer can be formed
Liquid is of great significance.
And the exploitation of high-voltage electrolyte essentially consists in the exploitation of additive and the optimization of solvent, it is therefore, a kind of there is an urgent need for proposing
The electrochemical window of electrolyte can be effectively widened, electrode interface protective layer is formed, effectively inhibits electrolyte in cyclic process
Oxygenolysis occurs and destruction is generated to cathode material structure, improves the operating voltage of battery, and it is steady to improve battery cycle of higher pressure
Qualitative electrolysis additive, and the lithium battery electrolytes comprising the electrolysis additive and lithium battery.
Invention content
(1) technical problems to be solved
In view of the deficiencies of the prior art, an object of the present invention is to provide a kind of electrolysis additive, which adds
Add agent that there is good oxidative resistance and anti-fire characteristic, protective film can be formed in positive electrode surface, effectively inhibited in electrolyte
Organic solvent oxygenolysis and the destruction to cathode material structure occur in cyclic process, widened the electrochemistry of electrolyte
Window, has widened the operating voltage range of battery, and improves the operating voltage of battery, so that it is may be up to 4.5~5V, and improve
The stability of battery cycle of higher pressure.
The second object of the present invention is to provide a kind of lithium battery electrolytes including above-mentioned electrolysis additive, the electrolyte
With wide electrochemical window, there is good cycle and security performance under higher voltage.
The third object of the present invention is to provide a kind of lithium battery including above-mentioned lithium battery electrolytes, which can be resistant to more
High voltage has good cycle and security performance under higher voltage.
(2) technical solution
In order to achieve the above object, the present invention uses following technical scheme：
One of the objects of the present invention is to provide a kind of electrolysis additive, the additive includes compound shown in formula I
At least one of：
Wherein, R1、R2、R3It is selected from alkenyl, aromatic radical, carbon atom number C1~C13Alkyl, carbon atom number C1~C13
Halogenated alkyl in one kind.
According to the present invention, the additive includes：Three (2,2,2- trifluoroethyls) phosphite esters, triphenyl phosphite, Asia
Trimethyl phosphate and triallyl phosphite ester.
The second object of the present invention is to provide a kind of lithium battery electrolytes, including basic electrolyte and electrolysis additive,
The electrolysis additive includes at least one of compound shown in formula I：
Wherein, R1、R2、R3It is selected from alkenyl, aromatic radical, carbon atom number C1~C12Alkyl, carbon atom number C1~C13
Halogenated alkyl in one kind.
According to the present invention, the electrolysis additive includes：Three (2,2,2- trifluoroethyls) phosphite esters, phosphorous triphenyl phosphate
Ester, Trimethyl phosphite and triallyl phosphite ester.
According to the present invention, the electrolysis additive account for the basic electrolyte by percentage to the quality 0.1~
10%.
According to the present invention, the electrolysis additive account for the basic electrolyte by percentage to the quality 0.5~
3%.
According to the present invention, the basic electrolyte includes lithium salts and organic solvent, and the organic solvent includes ethylene carbonate
Ester (EC), fluorinated ethylene carbonate (FEC), diethyl carbonate (DEC) and dimethyl carbonate (DMC).
According to the present invention, the ethylene carbonate, fluorinated ethylene carbonate, diethyl carbonate and dimethyl carbonate quality
Compare EC:FEC:DEC:DMC is 1~2:1~2:1~2:2~4.
According to the present invention, the lithium salts is selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), lithium perchlorate
(LiClO4At least one of)；Wherein, a concentration of 0.8~1.5mol/ of the lithium ion provided in the basic electrolyte
L。
The third object of the present invention is to provide a kind of lithium battery, including anode, cathode, diaphragm and electrolyte, the electrolysis
Liquid is the lithium battery electrolytes of any description above.
(3) advantageous effect
Compared with prior art, the present invention at least has the advantages that：
The electrolysis additive of the present invention has higher oxidisability than the organic solvent molecule of electrolyte, in lithium battery
Electrochemical oxidation can preferentially occur for positive electrode surface, form SEI protective films in positive electrode surface, have to effectively inhibit in electrolyte
Oxygenolysis and the destruction to cathode material structure occur in cyclic process for solvent, have widened the electrochemical window of electrolyte
Mouthful, improve the stability of battery cycle of higher pressure.
The present invention, which includes the electrolyte of above-mentioned electrolysis additive, has wide electrochemical window, is applicable to 2.8~5V
Charging voltage, oxygenolysis will not occur for organic solvent under higher voltage (4.5~5V), ensure that basic electrolyte group
The stability divided makes have good cycle and security performance under higher voltage (4.5~5V) using its lithium battery, this
After carrying out charge and discharge cycles 200 times under charge-discharge magnification is 0.5C, circulation volume retention rate improves the lithium battery of invention
15% or more.
Specific implementation mode
The present invention provides a kind of lithium battery electrolytes additive, additive includes at least one in compound shown in formula I
Kind：
Wherein, R1、R2、R3It is selected from alkenyl, aromatic radical, carbon atom number C1~C13Alkyl, carbon atom number C1~C13
Halogenated alkyl in one kind.
Specifically, alkenyl is selected from alkenyl or its isomers and fluoro object；Preferably, alkenyl be selected from vinyl, acrylic,
One kind in cyclobutenyl, difluoroethylene base, fluoro isopropenyl, trifluoro-propenyl, trifluorobutene base.
In the one kind or phenyl, alkyl phenyl, alkenyl phenyl of aromatic radical in phenyl, alkyl phenyl, alkenyl phenyl
Any isomers, fluoro object；Preferably, aromatic radical be selected from phenyl, tolyl, trimethylphenyl, ethylbenzene, diethyl phenyl,
In propyl phenyl, three propyl phenyls, fluoroform phenyl, trifluoro ethylbenzene, fluorine propyl phenyl, trifluoro propyl phenyl, one kind in pentafluorophenyl group.
Alkyl is selected from C1~C13Alkyl or its isomers, fluoro object；Preferably, alkyl is selected from methyl, ethyl, positive third
Base, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, dodecyl, ten
Trialkyl, trifluoromethyl, trifluoroethyl, trifluoro propyl, triRuorobutyl, three fluorine amyl groups, trifluorododecyl, trifluoro tridecyl
In one kind.
Preferably, additive of the invention is three (2,2,2- trifluoroethyl) phosphite esters (such as formula (1)), phosphorous triphenyl phosphate
Any one of ester (such as formula (2)), Trimethyl phosphite (such as formula (3)), triallyl phosphite ester (such as formula (4)) are several
Combination.
In addition, the present invention provides a kind of lithium battery electrolytes, including basic electrolyte and with above-described electrolyte
Additive.Wherein, electrolysis additive account for basic electrolyte by percentage to the quality 0.1~10%, preferably 0.5~
3%, more preferably, electrolysis additive accounts for by percentage to the quality 1%, 1.5%, any of 2% of basic electrolyte.
When electrolysis additive is less than 0.1%, the amount of additive is inadequate, cannot form enough SEI films, to inhibit to have
Destruction of the solvent to positive electrode；When electrolysis additive is more than 10%, the SEI film thicknesses of formation are excessive, can not only increase
The internal resistance of battery itself, and the conduction velocity of lithium ion can be hindered, so as to cause the rapid decaying of capacity, and then influence battery
Cycle life；Therefore, the additive amount of electrolysis additive of the invention accounts for existing by percentage to the quality for basic electrolyte
When in 0.1%~10% range, sufficiently thick SEI films can have both been formed, have inhibited destruction of the organic solvent to positive electrode, and not
The internal resistance of battery itself can be increased, the conduction velocity of lithium ion, best results will not be hindered.
In the present invention, basic electrolyte includes organic solvent and lithium salts, it is preferable that organic solvent includes ethylene carbonate
Ester, fluorinated ethylene carbonate, diethyl carbonate and dimethyl carbonate, ethylene carbonate, fluorinated ethylene carbonate, diethyl carbonate
Mass ratio with dimethyl carbonate is 1~2:1~2:1~2:2~4.It is highly preferred that ethylene carbonate, fluorinated ethylene carbonate,
The mass ratio of diethyl carbonate and dimethyl carbonate is 1:1:1:2、1:2:1:2、2:1:2:4、1:2:2:Any of 3, more
Preferably, the mass ratio of ethylene carbonate, fluorinated ethylene carbonate, diethyl carbonate and dimethyl carbonate is 1:1:1:2.
Lithium salts is selected from lithium hexafluoro phosphate, LiBF4, at least one of lithium perchlorate, lithium salts a concentration of 0.8~
1.5mol/L, it is preferable that a concentration of 1.0~1.35mol/L of lithium salts, for example, a concentration of 1.0mol/L, 1.20mol/ of lithium salts
L, any of 1.30mol/L.
The preparation method of the lithium battery electrolytes of the present invention does not have particular/special requirement, as long as by each group of lithium battery electrolytes
Divide and be uniformly mixed, for example, can first be uniformly mixed organic solvent, lithium salts is then added and is uniformly mixed, it finally again will be above-mentioned
Lithium battery electrolytes additive be uniformly mixed.
The present invention also provides a kind of lithium battery, including anode, cathode, diaphragm and electrolyte, electrolyte is above-mentioned electrolysis
Liquid.Preferably, the active material in positive electrode can be selected from the compound lithium metal oxide containing three kinds of nickel, cobalt and manganese elements,
Nickel in wherein compound lithium metal oxide：Cobalt：The molar ratio of manganese is 8：1：1, such as：LiNi0.8Co0.1Mn0.1O2.Negative material
In active material can be selected from least one of lithium metal, lithium alloy.
The preparation method and assembling form of the lithium battery of the present invention do not have particular/special requirement, can be normal in field of lithium
Rule selection.Preferably, the present invention can be assembled into button lithium battery.For example, aluminium foil may be selected in the plus plate current-collecting body of lithium battery, bear
Copper foil may be selected in pole collector, and ceramic diaphragm etc. may be selected in diaphragm.
The above-mentioned electrolysis additive of the present invention has higher oxidisability than the organic solvent molecule of electrolyte, in lithium electricity
Electrochemical oxidation can preferentially occur for the positive electrode surface in pond, interface protective film be formed in positive electrode surface, to effectively inhibit electrolysis
Oxygenolysis and the destruction to cathode material structure occur in cyclic process for organic solvent in liquid, have widened the electrification of electrolyte
Window is learned, the stability of battery cycle of higher pressure is improved.
The present invention, which includes the electrolyte of above-mentioned electrolysis additive, has wide electrochemical window, is applicable to 2.8~5V
Charging voltage, oxygenolysis will not occur under higher voltage (4.5~5V), ensure that the stability of component, make use
There is its lithium battery good cycle and security performance, lithium battery of the invention to fill under higher voltage (4.5~5V)
After discharge-rate is progress charge and discharge cycles under 0.5C 200 times, circulation volume retention rate improves 15% or more.
Present invention be described in more detail by the following examples, but the invention is not limited in following embodiments.
Embodiment 1
The triphenyl phosphite of 0.1wt% is dissolved in as electrolysis additive in basic electrolyte, wherein basis electricity
The molal weight ratio of organic solvent ethylene carbonate, fluorinated ethylene carbonate, diethyl carbonate and dimethyl carbonate in solution liquid
EC:FEC:DEC:DMC is 1:1:1:2, lithium salts LiPF6Molar concentration be 1mol/L, with LiNi0.8Co0.1Mn0.1O2As anode
Active material, for lithium metal as negative electrode active material, positive and negative anodes collector is respectively adopted aluminium foil and copper foil, diaphragm using ceramics every
Film is assembled into the button cell of 811/ lithium metal of ternary.
Embodiment 2
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the triphenyl phosphite of 0.5wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition is same as Example 1.
Embodiment 3
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the triphenyl phosphite of 2wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition is same as Example 1.
Embodiment 4
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the triphenyl phosphite of 5wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition is same as Example 1.
Embodiment 5
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For three (2,2,2- trifluoroethyl) phosphite esters of 0.1wt%, remaining condition is same as Example 1.
Embodiment 6
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For three (2,2,2- trifluoroethyl) phosphite esters of 0.5wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition
It is same as Example 1.
Embodiment 7
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For three (2,2,2- trifluoroethyl) phosphite esters of 2wt%, remaining condition is same as Example 1.
Embodiment 8
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For three (2,2,2- trifluoroethyl) phosphite esters of 5wt%, remaining condition is same as Example 1.
Embodiment 9
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the Trimethyl phosphite of 1wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition is same as Example 1.
Embodiment 10
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the Trimethyl phosphite of 1.5wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition is same as Example 1.
Embodiment 11
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 9, except that electrolysis additive
For the Trimethyl phosphite of 3wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition is same as Example 1.
Embodiment 12
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the Trimethyl phosphite of 5wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition is same as Example 1.
Embodiment 13
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the Trimethyl phosphite of 7wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition is same as Example 1.
Embodiment 14
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the Trimethyl phosphite of 10wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition is same as Example 1.
Embodiment 15
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the triallyl phosphite ester of 2wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition and 1 phase of embodiment
Together.
Embodiment 16
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the triallyl phosphite ester of 3wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition and 1 phase of embodiment
Together.
Embodiment 17
The button cell that 811/ lithium metal of ternary is prepared according to the method for embodiment 1, except that electrolysis additive
For the triallyl phosphite ester of 5wt%, lithium salts LiPF6Molar concentration be 1.2mol/L, remaining condition and 1 phase of embodiment
Together.
Comparative example 1
Basic electrolyte and lithium battery are prepared according to the method for embodiment 1, except that it is added without electrolysis additive,
Remaining condition is same as Example 1.
Comparative example 2
Basic electrolyte and lithium battery are prepared according to the method for embodiment 5, except that it is added without electrolysis additive,
Remaining condition is same as Example 5.
Comparative example 3
Basic electrolyte and lithium battery are prepared according to the method for embodiment 9, except that it is added without electrolysis additive,
Remaining condition is same as Example 9.
Comparative example 4
Basic electrolyte and lithium battery are prepared according to the method for embodiment 15, except that being added without electrolyte addition
Agent, remaining condition are identical as embodiment 15.
Testing example 1-17 and comparative example 1-4
After embodiment 1-17 and comparative example the 1-4 lithium battery prepared are stood 8h, in 25 DEG C of room temperature, potential range 2.8-
5V, after charge-discharge magnification is progress charge and discharge cycles under 0.5C 200 times, according to the test method of conventional battery capacity retention rate
The test of lithium battery capacity retention rate is carried out, the results are shown in Table 1.
Table 1
Embodiment 1, embodiment 5, embodiment 9, embodiment 15, which are can be seen that, from the test result of table 1 is added with different electricity
Lithium battery prepared by solution solution additive is electric to the correspondings lithium for being not added with electrolysis additive preparation of comparative example 4 with comparative example 1 respectively
Pond is compared, after carrying out charge and discharge cycles 200 times under charge-discharge magnification is 0.5C, capacity retention rate improve at least 15% with
On.This is because applying phosphite ester compound in high-voltage electrolyte, additive takes part in positive film formation reaction, phosphorous
Acid esters compound has higher oxidisability than organic solvent molecule, and electrochemical oxidation, shape can preferentially occur in positive electrode surface
At the interfacial film stablized and homogeneity is good electrolyte component is ensure that inhibit the decomposition of organic dissolution in electrolyte
Stability reduces the generation of side reaction between electrolyte and positive electrode, maintains the stability at electrode/electrolyte interface,
Cathode film layer impedance and charge transfer impedance of the material in cyclic process are advantageously reduced, is beneficial to lithium ion in cyclic process
In in electrode reversibly intercalation/deintercalation, effectively improve the chemical property of high-energy density positive electrode.
Embodiment 1-17 used the present invention lithium battery potential range be 2.8-5V, charge-discharge magnification be 0.5C under into
Very high capacity retention rate is maintained after row charge and discharge cycles 200 times, there is excellent high voltage withstanding property, especially, embodiment
The 16 lithium battery capacity retention rates prepared using triallyl phosphite esters reach highest, 95% or more, this may be because
In cyclic process, allyl may crosslink electric polymerization reaction, and obtained product covers electrode surface, be formed uniform
SEI films, while allyl can significantly improve coulombic efficiency, after recycling for a long time, still have very high capacity retention ratio.
Three (2,2,2- trifluoroethyl) phosphite esters that embodiment 5-8 is used contain fluorine element, can be used as being total to for electrolyte
Solvent improves the high voltage performance of electrolyte solvent system, while its characteristic with high-flash or without flash-point, is conducive to electricity
Pond in high temperature, the safety under abuses state such as overcharge, and there is higher lithium battery capacity retention rate.
The above described is only a preferred embodiment of the present invention, being not the limitation for doing other forms to the present invention, appoint
What those skilled in the art can be changed or be modified as the equivalence enforcement of equivalent variations using technology contents disclosed above
Example.But it is every without departing from technical solution of the present invention content, according to the technical essence of the invention to appointing made by above example
What simple modification, equivalent variations and remodeling, still falls within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of electrolysis additive, which is characterized in that the additive includes at least one of compound shown in formula I：
Wherein, R1、R2、R3It is selected from alkenyl, aromatic radical, carbon atom number C1~C13Alkyl, carbon atom number C1~C13Halogen
One kind in substituted alkyl.
2. electrolysis additive as described in claim 1, which is characterized in that the additive includes：Three (2,2,2- trifluoro second
Base) phosphite ester, triphenyl phosphite, Trimethyl phosphite and triallyl phosphite ester.
3. a kind of lithium battery electrolytes, including basic electrolyte and electrolysis additive, which is characterized in that the electrolyte addition
Agent includes at least one of compound shown in formula I：
Wherein, R1、R2、R3It is selected from alkenyl, aromatic radical, carbon atom number C1~C12Alkyl, carbon atom number C1~C13Halogen
One kind in substituted alkyl.
4. lithium battery electrolytes as claimed in claim 3, which is characterized in that the electrolysis additive includes：Three (2,2,2-
Trifluoroethyl) phosphite ester, triphenyl phosphite, Trimethyl phosphite and triallyl phosphite ester.
5. lithium battery electrolytes as claimed in claim 4, which is characterized in that the electrolysis additive accounts for the basis electrolysis
By percentage to the quality the 0.1~10% of liquid.
6. lithium battery electrolytes as claimed in claim 5, which is characterized in that the electrolysis additive accounts for the basis electrolysis
By percentage to the quality the 0.5~3% of liquid.
7. lithium battery electrolytes as claimed in claim 3, which is characterized in that the basic electrolyte includes lithium salts and organic molten
Agent, the organic solvent include ethylene carbonate, fluorinated ethylene carbonate, diethyl carbonate and dimethyl carbonate.
8. lithium battery electrolytes as claimed in claim 7, which is characterized in that the ethylene carbonate, fluorinated ethylene carbonate,
The mass ratio of diethyl carbonate and dimethyl carbonate is 1~2:1~2:1~2:2~4.
9. lithium battery electrolytes as claimed in claim 7, which is characterized in that the lithium salts is selected from lithium hexafluoro phosphate, tetrafluoro boron
At least one of sour lithium, lithium perchlorate；Wherein, a concentration of the 0.8 of the lithium ion provided in the basic electrolyte~
1.5mol/L。
10. a kind of lithium battery, including anode, cathode, diaphragm and electrolyte, which is characterized in that the electrolyte is claim
Any lithium battery electrolytes of 3-9.
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| CN109818062A (en) * | 2019-03-08 | 2019-05-28 | 江西星盈科技有限公司 | Ternary lithium ion battery and its electrolyte |
| CN109860704A (en) * | 2018-11-13 | 2019-06-07 | 东莞东阳光科研发有限公司 | Positive film for additive, electrolyte and lithium ion battery comprising it |
| CN110048162A (en) * | 2019-04-04 | 2019-07-23 | 李秀艳 | High-voltage electrolyte additive, electrolyte and battery containing the additive |
| CN110534807A (en) * | 2019-09-29 | 2019-12-03 | 河南省法恩莱特新能源科技有限公司 | A kind of LiNi0.5Mn1.5O4Positive lithium-ion battery electrolytes and preparation method |
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