CN107768719A - A kind of lithium-ion battery electrolytes and lithium ion battery - Google Patents
A kind of lithium-ion battery electrolytes and lithium ion battery Download PDFInfo
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- CN107768719A CN107768719A CN201710978247.4A CN201710978247A CN107768719A CN 107768719 A CN107768719 A CN 107768719A CN 201710978247 A CN201710978247 A CN 201710978247A CN 107768719 A CN107768719 A CN 107768719A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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 invention belongs to technical field of lithium ion, more particularly to a kind of lithium-ion battery electrolytes and lithium ion battery, the present invention is added with the class additive of A, B, C, D tetra- in the electrolytic solution, and wherein for additive A as cathode film formation additive, it is the premise for ensureing electrolyte long circulating performance；Additive B can improve cell output, reduce the impedance in cyclic process；Temperature rise when cooperative effect improves the low temperature discharge platform of battery, reduction heavy-current discharge process between addition of C and additive B be present；Additive D can be to SEI films formation rise regulating and controlling effect, suppress B classes and C classes additive excessively participates in the formation of SEI films, with high discharging efficiency while battery is ensured with higher discharge platform, additive D causes battery to have higher charged maintenance dose during high-temperature storage and heavy-current discharge simultaneously, suppresses the increase of battery impedance；In addition, electrolyte of the present invention has anti-overcharge performance in the case where being added without anti-overcharge additive.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of lithium-ion battery electrolytes and power-type cylinder
Lithium ion battery.
Background technology
Power-type lithium ion battery requires that lithium battery disclosure satisfy that the high current charge-discharge ability of moment and continuation, uses
Process has relatively low temperature rise and wider operating temperature range, while has higher security performance.
Quickly realize that the diffusion of lithium ion subtracts for power type battery electrolyte, it is necessary to during heavy-current discharge
Small polarization, the impedance of SEI films is reduced, improve electrolyte has higher electrical conductivity in wide temperature range, in -20 DEG C of environment of low temperature
Under can still realize the discharge capability of big multiplying power；Raised simultaneously during high current use along with battery temperature and require electrolysis
Liquid can meet the normal work under 60-80 DEG C of hot conditions；In addition, it is desirable to which battery fluid high-temperature storage and high temperature high current use
During internal resistance change it is relatively low to ensure that battery has a higher output performance, and as far as possible during reduction battery fluid use
Temperature rise to lift cycle life.However, in terms of power-type cylindrical battery electrolyte, take into account low temperature and the big multiplying power of high temperature is defeated
With preferable storge quality to ensure to follow with relatively low internal resistance rate of change and length during battery use while going out performance
Ring life capacity, it is a big difficult point.
Power-type cylindrical battery security performance during high rate charge-discharge can be also affected, and especially big multiplying power is filled
Because temperature raises explosion-proof valve may be caused to flick in electric process, persistently overcharge and cause the safety problems such as battery explosion, at present solution
Certainly anti-overcharge safety problem usually adds a certain amount of anti-overcharge additive, but most of anti-overcharge additives in the electrolytic solution
Introducing on the one hand can bring the increase of battery impedance, reduce output performance, while anti-overcharge additive can be to the circulation of battery
Life-span, storge quality bring irreversible influence.
Wherein, Chinese patent CN105336986 provides a kind of power-type containing FEC, TMSB and DFOB/BOB composition
Low-temperature electrolyte, realize electrolyte has higher electrical conductivity and preferable output performance at low ambient temperatures；But research hair
Now exist during the electrolyte use TMSB and BOB etc. excessively participate in film forming the problem of, negative pole SEI films are thicker, impedance still compared with
Greatly, so as to causing battery low temperature discharge platform to be had clear improvement compared to conventional electrolysis liquid and the discharging efficiency of electrolyte and unknown
The problem of aobvious increase, while there is open defect in the high-temperature storage performance of the electrolyte, capacity after the 60 DEG C long-term storage of its high temperature
Keep and recovery capability is relatively low, it is often more important that it is anti-overcharge in big multiplying power charging process that the program not can solve battery
Performance, potential safety hazard be present.
The content of the invention
It is an object of the invention to：It is higher for existing power type battery electrolyte cathode film formation impedance, put though improving
Level platform but discharging efficiency is unsatisfactory, while high temperature long-term storage performance especially capacity is kept and recovery capability is relatively low, greatly
The problems such as temperature rise is higher during multiplying power discharging, and the security performance such as anti-overcharge is bad, the present invention provide one kind and can be added without
The power-type lithium ion battery electrolyte to be solved the above problems on the premise of anti-overcharge additive, meets power type battery very well
Requirement of the electrolyte to wide warm area high current charge-discharge ability, temperature rise control, high-temperature storage and anti-overcharge performance.
To achieve these goals, the present invention uses following technical scheme：
A kind of lithium-ion battery electrolytes, including Non-aqueous Organic Solvents, lithium salts and additive, the additive include adding
Add agent A, additive B, addition of C and additive D；The additive A is fluorinated ethylene carbonate, the fluoro ethylene carbonates of 1,2- bis-
One or both of ester, the additive B are phosphorous and/or boracic organic esterses, and the addition of C is lithium salts
Type additive, the additive D are the nitrile compounds with 2~3 itrile group functional groups.
Preferably, the addition of the additive A accounts for the 0.5~10% of electrolyte gross mass, the addition of the additive B
Amount accounts for the 0.1~3% of electrolyte gross mass, and the addition of the addition of C accounts for the 0.1~2% of electrolyte gross mass, described to add
Agent D addition is added to account for the 0.3~3% of electrolyte gross mass.
Preferably, the additive B is three (trimethyl silane) phosphates, three (trimethyl silane) borates, three (front threes
Base silane) phosphite ester, Trimethylsilyl trifluoromethanesulfonate, trifluoroacetic acid trimethylsilyl group, three (triethyl silicane) phosphates,
Three (triethyl silicane) borates, three (trimethyl silane) phosphite esters, three (triethyl silicane) phosphite esters, boric acid three (six
Fluorine isopropyl) ester, three (hexafluoro isopropyl) phosphates, at least one of three (hexafluoro isopropyl) phosphite esters.
Preferably, the addition of C is difluorophosphate, difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, the double (grass of difluoro
Acid group) close at least one of lithium phosphate, LiBF4,4,5- dinitrile -2- trifluoromethyl imidazoles lithiums.
Preferably, the additive D is adiponitrile, succinonitrile, dimethyl-penten dintrile, the nitrile of 1,3,6- hexane three, pimelic dinitrile
At least one of.
Preferably, the additive is vinylene carbonate also including Low ESR additive E, the Low ESR additive E
At least one of VC, propylene sulfite PS, butylene sulfite BS, ethyl sulfate DTD, the Low ESR additive E
Addition account for the 0.1~1.5% of electrolyte gross mass.
Preferably, the Non-aqueous Organic Solvents be dimethyl carbonate DMC, diethyl carbonate DEC, methyl ethyl carbonate EMC,
The two or more mixtures mixed in any proportion in propene carbonate PC, ethylene carbonate EC and methyl propyl carbonate MPC；Institute
State Non-aqueous Organic Solvents account for electrolyte gross mass 65%~85%.
Preferably, the lithium salts is lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine sulfimides
At least one of lithium, LiBF4, double trifluoromethanesulfonimide lithiums；The lithium salts account for electrolyte gross mass 10%~
20%.
Another object of the present invention is to a kind of, there is provided lithium ion battery, including by positive plate, barrier film and negative plate according to
The core and electrolyte that sublevel poststack is wound in the same direction, the electrolyte be any of the above-described section described in lithium from
Sub- battery electrolyte.
Preferably, the positive electrode of the positive plate is included in cobalt acid lithium, LiMn2O4, nickel ion doped, nickle cobalt lithium manganate
At least one, and also include the lithium carbonate that weight/mass percentage composition is 0.1~1%.Lithium carbonate is when overcharging due to supercharging oxidation production
Gas, explosion-proof valve can be made to shift to an earlier date pressure release, further improve the overcharge safety energy of battery.
Preferably, the negative material of the negative plate be Delanium, native graphite, soft carbon, hard carbon, silicium cathode material,
At least one of silicon-carbon cathode material.
Preferably, the barrier film is ceramic diaphragm, and the porosity of the barrier film is 40~60%, and the core is multi pole ears
Core, further to reduce internal resistance.
Preferably, the normal temperature operating voltage of the battery is 3.0~4.2V；Big multiplying power continuous discharge electric current is 10~15C,
The electric current that sparks is 20C.
The beneficial effects of the present invention are：The present invention is added with the class additive of A, B, C, D tetra- in the electrolytic solution, wherein adding
Agent A is mainly cathode film formation additive, and it is the premise for ensureing electrolyte long circulating performance；It is defeated that additive B can improve battery
Go out performance, reduce the impedance during circulating battery；Cooperative effect between addition of C and additive B be present and improve the low of battery
Temperature rise when warm discharge platform, reduction heavy-current discharge process；Additive D can be to SEI films formation rise regulating and controlling effect, suppress
B classes and C classes additive excessively participate in the formation of SEI films, with high electric discharge while ensureing battery with higher discharge platform
Efficiency, while additive D causes battery to have higher charged maintenance dose during high-temperature storage and heavy-current discharge, suppresses
The increase of battery impedance.In addition, the power-type cylindrical battery electrolyte being made up of above-mentioned additive A, B, C, D is being added without anti-mistake
The anti-overcharge performance of battery can be ensured on the premise of filling additive.
Embodiment
To make technical scheme and advantage clearer, below in conjunction with specific embodiment, to the skill of the present invention
Art scheme is clearly and completely described, it is clear that and described embodiment is part of the embodiment of the present invention, rather than all
Embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art institute under the premise of creative work is not made
The every other embodiment obtained, belongs to the scope of protection of the invention.
Embodiment 1
The preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 3.0% that mass fraction is added in mixed solution
Fluorinated ethylene carbonate FEC, 1.0% di-oxalate lithium borate LiBOB, 0.5% three (trimethyl silane) borate TMSB,
0.3% LiBF4 LiBF4, 1.5% succinonitrile SN, it is slow added into the LiPF that mass fraction is 16%6, stirring is extremely
It is completely dissolved, and obtains lithium-ion battery electrolytes.
The preparation of lithium ion battery：
By positive active material nickle cobalt lithium manganate, lithium carbonate, conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF)
After in mass ratio 95: 1: 2: 2 are thoroughly mixed uniformly in 1-METHYLPYRROLIDONE dicyandiamide solution, coated on being dried on Al paper tinsels
Dry, cold pressing, obtains positive plate.
By negative electrode active material Delanium, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickening agent carboxymethyl
After sodium cellulosate (CMC) is thoroughly mixed uniformly according to mass ratio 96: 2: 1: 1 in deionized water solvent system, it is coated on
Dry, be cold-pressed on Cu paper tinsels, obtain negative plate.
Barrier film for basement membrane (12 μm) and is used as in the nano oxidized aluminized coating of coating on base films (2 μm) using polyethylene (PE).
Winding obtains naked battery core in the same direction after positive plate, barrier film, negative plate are stacked gradually, then by naked battery core
It is placed in box hat, injects the electrolyte of preparation and encapsulated, obtain the cylindrical lithium ion battery of model 18650.
Embodiment 2
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 5.0% that mass fraction is added in mixed solution
Fluorinated ethylene carbonate FEC, 1.0% difluoro double (oxalates) close lithium phosphate, 0.5% three (trimethyl silane) phosphates
TMSP, 0.3% LiBF4 LiBF4, 1.5% succinonitrile SN, it is slow added into the LiPF that mass fraction is 16%6, stir
Mix to it and be completely dissolved, obtain lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 3
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 5.0% that mass fraction is added in mixed solution
Fluorinated ethylene carbonate FEC, 1.0% difluoro double (oxalates) close lithium phosphate, 0.5% three (trimethyl silane) phosphates
TMSP, 1.0% difluorophosphate, 1.5% adiponitrile ADN, it is slow added into the LiPF that mass fraction is 16%6, stirring
It is completely dissolved to it, obtains lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 4
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 5.0% that mass fraction is added in mixed solution
Fluorinated ethylene carbonate FEC, 0.5% difluoro double (oxalates) close lithium phosphate, 0.5% three (trimethyl silane) phosphates
TMSP, 0.3% difluorophosphate, 1.5% adiponitrile ADN, it is slow added into the LiPF that mass fraction is 16%6, stirring
It is completely dissolved to it, obtains lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 5
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 5.0% that mass fraction is added in mixed solution
Fluorinated ethylene carbonate FEC, 0.5% difluoro double (oxalates) conjunction lithium phosphate, 0.5% three (hexafluoro isopropyl) phosphates,
0.3% difluorophosphate, 1.5% adiponitrile ADN, it is slow added into the LiPF that mass fraction is 16%6, stir complete to its
Fully dissolved, obtain lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 6
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 5.0% that mass fraction is added in mixed solution
Fluorinated ethylene carbonate FEC, 1.0% difluorine oxalic acid boracic acid lithium LiDFOB, 0.5% three (trimethyl silane) borates
TMSB, 0.3% difluorophosphate, 1.5% succinonitrile SN, it is slow added into the LiPF that mass fraction is 16%6, stirring is extremely
It is completely dissolved, and obtains lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 7
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 5.0% that mass fraction is added in mixed solution
1,2- difluorinated ethylene carbonate, 1.5% difluorine oxalic acid boracic acid lithium LiDFOB, 0.5% three (trimethyl silane) borates
TMSB, 0.1% 4,5- dinitrile -2- trifluoromethyl imidazoles lithiums, 1.5% dimethyl-penten dintrile, it is slow added into quality point
Number is 16% LiPF6, stir to it and be completely dissolved, obtain lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 8
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 5.0% that mass fraction is added in mixed solution
1,2- difluorinated ethylene carbonate, 1.0% difluorine oxalic acid boracic acid lithium LiDFOB, 0.5% three (triethyl silicane) borates,
0.5% 4,5- dinitrile -2- trifluoromethyl imidazoles lithiums, the 1 of 2.0%, the nitrile of 3,6- hexane three, being slow added into mass fraction is
16% LiPF6, stir to it and be completely dissolved, obtain lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 9
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 8.0% that mass fraction is added in mixed solution
1,2- difluorinated ethylene carbonate, 1.0% di-oxalate lithium borate LiBOB, 1.0% Trimethylsilyl trifluoromethanesulfonate,
0.5% 4,5- dinitrile -2- trifluoromethyl imidazoles lithiums, 2.0% pimelic dinitrile, it is 16% to be slow added into mass fraction
LiPF6, stir to it and be completely dissolved, obtain lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 10
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 5.0% that mass fraction is added in mixed solution
Fluorinated ethylene carbonate FEC, 1.0% di-oxalate lithium borate LiBOB, 1.0% three (triethyl silicane) borates, 0.5%
Difluorophosphate, 1.5% pimelic dinitrile, be slow added into mass fraction be 16% LiPF6, stir to it and be completely dissolved,
Obtain lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 11
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 3.0% that mass fraction is added in mixed solution
Fluorinated ethylene carbonate FEC, 1.0% di-oxalate lithium borate LiBOB, 0.5% three (trimethyl silane) borate TMSB,
0.3% LiBF4 LiBF4, 1.5% succinonitrile SN, 1.0% vinylene carbonate VC, it is slow added into quality point
Number is 16% LiPF6, stir to it and be completely dissolved, obtain lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 12
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 3.0% that mass fraction is added in mixed solution
Fluorinated ethylene carbonate FEC, 1.0% di-oxalate lithium borate LiBOB, 0.5% three (trimethyl silane) borate TMSB,
0.3% LiBF4 LiBF4, 1.5% succinonitrile SN, 1.5% propylene sulfite PS, it is slow added into quality point
Number is 16% LiPF6, stir to it and be completely dissolved, obtain lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Embodiment 13
As different from Example 1, the preparation of electrolyte：
In the glove box (moisture ＜ 10ppm, oxygen ＜ 1ppm) full of argon gas, by ethylene carbonate EC, carbonic acid diformazan
Ester DMC, methyl ethyl carbonate EMC are with 20:60:20 mass ratioes are well mixed, and it is 3.0% that mass fraction is added in mixed solution
Fluorinated ethylene carbonate FEC, 1.0% di-oxalate lithium borate LiBOB, 0.5% three (trimethyl silane) borate TMSB,
0.3% LiBF4 LiBF4, 1.5% succinonitrile SN, 0.5% ethyl sulfate DTD, it is slow added into quality point
Number is 16% LiPF6, stir to it and be completely dissolved, obtain lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Comparative example 1
As different from Example 1, the preparation of electrolyte：In glove box (moisture ＜ 10ppm, oxygen ＜ full of argon gas
In 1ppm), by ethylene carbonate EC, dimethyl carbonate DMC, methyl ethyl carbonate EMC with 20:60:20 mass ratioes are well mixed,
Fluorinated ethylene carbonate FEC, the 1.0% di-oxalate lithium borate LiBOB that mass fraction is 3.0% are added in mixed solution,
0.5% three (trimethyl silane) borate TMSB, it is slow added into the LiPF that mass fraction is 16%6, stir complete to its
Dissolving, obtains lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Comparative example 2
As different from Example 1, the preparation of electrolyte：In glove box (moisture ＜ 10ppm, oxygen ＜ full of argon gas
In 1ppm), by ethylene carbonate EC, dimethyl carbonate DMC, methyl ethyl carbonate EMC with 20:60:20 mass ratioes are well mixed,
Fluorinated ethylene carbonate FEC, the 1.0% difluorine oxalic acid boracic acid lithium LiDFOB that mass fraction is 3.0% are added in mixed solution,
0.5% three (trimethyl silane) borate TMSB, it is slow added into the LiPF that mass fraction is 16%6, stir complete to its
Dissolving, obtains lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Comparative example 3
As different from Example 1, the preparation of electrolyte：In glove box (moisture ＜ 10ppm, oxygen ＜ full of argon gas
In 1ppm), by ethylene carbonate EC, dimethyl carbonate DMC, methyl ethyl carbonate EMC with 20:60:20 mass ratioes are well mixed,
Fluorinated ethylene carbonate FEC, the 1.0% di-oxalate lithium borate LiBOB that mass fraction is 3.0% are added in mixed solution,
0.5% difluorine oxalic acid boracic acid lithium LiDFOB, it is slow added into the LiPF that mass fraction is 16%6, stir to it and be completely dissolved,
Obtain lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
Comparative example 4
As different from Example 1, the preparation of electrolyte：In glove box (moisture ＜ 10ppm, oxygen ＜ full of argon gas
In 1ppm), by ethylene carbonate EC, dimethyl carbonate DMC, methyl ethyl carbonate EMC with 20:60:20 mass ratioes are well mixed,
Fluorinated ethylene carbonate FEC, the 1.0% di-oxalate lithium borate LiBOB that mass fraction is 3.0% are added in mixed solution,
0.5% difluorine oxalic acid boracic acid lithium LiDFOB, 2% cyclohexyl benzene CHB, it is slow added into the LiPF that mass fraction is 16%6,
Stirring is completely dissolved to it, obtains lithium-ion battery electrolytes.
Remaining is repeated no more here with embodiment 1.
The cycle performance to embodiment 1~13 and the progress battery of comparative example 1~4 is tested respectively, high-temperature storage performance is tested,
And overcharge safety can be tested, test result is shown in Table 1.
The cycle performance of battery of the embodiment of table 1 and comparative example, storge quality and security performance test result
From the test result of table 1, using the normal temperature 1C/1C cycle performances of the lithium ion battery of electrolyte of the present invention,
High temperature cyclic performance, 70 DEG C of storage internal resistance changes in 7 days of high temperature and capacity retention energy and anti-overcharge (3C overcharges test) performance (are removed
Outside comparative example 4) lithium ion battery using comparative example 1~4 is superior to (due to adding anti-overcharge additive in comparative example 4
CHB, can be by overcharging test, but its circulation and storge quality substantially deteriorate).Because the electrolysis in comparative example 1~3
The problem of TMSB and LiBOB etc. excessively participates in film forming during liquid use be present, negative pole SEI films are thicker, and impedance is still larger, cause
Capacity is kept after high temperature storage for a long time and recovery capability is relatively low；And the present invention adds added with the class of A, B, C, D tetra- in the electrolytic solution
As cathode film formation additive, it can ensure electrolyte long circulating performance for agent, wherein additive A；Additive B can improve electricity
Pond output performance, reduce the impedance in cyclic process；Cooperative effect between addition of C and additive B be present and improve the low of battery
Temperature rise when warm discharge platform, reduction heavy-current discharge process；Additive D can be to SEI films formation rise regulating and controlling effect, suppress
B classes and C classes additive excessively participate in the formation of SEI films, with high electric discharge while ensureing battery with higher discharge platform
Efficiency, while additive D causes battery to have higher charged maintenance dose during high-temperature storage and heavy-current discharge, suppresses
The increase of battery impedance；Therefore, possesses good cycle performance by the battery that is used in combination of the class additive of A, B, C, D tetra-
With high-temperature storage performance, while preferable anti-overcharge performance is also equipped with.In addition, can be with from embodiment 1 and embodiment 11~13
Find out, the cycle performance and high-temperature storage performance of battery can be further improved by further adding Low ESR additive E.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in above-mentioned embodiment, every those skilled in the art exist
Made any conspicuously improved, replacement or modification belong to protection scope of the present invention on the basis of the present invention.This
Outside, although having used some specific terms in this specification, these terms merely for convenience of description, not to the present invention
Form any restrictions.
Claims (10)
1. a kind of lithium-ion battery electrolytes, including Non-aqueous Organic Solvents, lithium salts and additive, it is characterised in that：It is described to add
Agent is added to include additive A, additive B, addition of C and additive D；The additive A is fluorinated ethylene carbonate, 1,2- difluoros
For one or both of ethylene carbonate, the additive B is phosphorous and/or boracic organic esterses, described to add
It is lithium salts type additive to add agent C, and the additive D is the nitrile compounds with 2~3 itrile group functional groups.
A kind of 2. lithium-ion battery electrolytes according to claim 1, it is characterised in that：The addition of the additive A
Account for the 0.5~10% of electrolyte gross mass, the addition of the additive B accounts for the 0.1~3% of electrolyte gross mass, described to add
Agent C addition is added to account for the 0.1~2% of electrolyte gross mass, the addition of the additive D accounts for the 0.3 of electrolyte gross mass
~3%.
A kind of 3. lithium-ion battery electrolytes according to claim 1, it is characterised in that：The additive B is three (front threes
Base silane) phosphate, three (trimethyl silane) borates, three (trimethyl silane) phosphite esters, trifluoromethanesulfonic acid trimethyl silicane
Ester, trifluoroacetic acid trimethylsilyl group, three (triethyl silicane) phosphates, three (triethyl silicane) borates, three (trimethyl silicanes
Alkane) phosphite ester, three (triethyl silicane) phosphite esters, boric acid three (hexafluoro isopropyl) ester, three (hexafluoro isopropyl) phosphates,
At least one of three (hexafluoro isopropyl) phosphite esters.
A kind of 4. lithium-ion battery electrolytes according to claim 1, it is characterised in that：The addition of C is difluoro phosphorus
Sour lithium, difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate, difluoro double (oxalates) close lithium phosphate, LiBF4,4,5- dintrile
At least one of base -2- trifluoromethyl imidazoles lithiums.
A kind of 5. lithium-ion battery electrolytes according to claim 1, it is characterised in that：The additive D be adiponitrile,
At least one of succinonitrile, dimethyl-penten dintrile, the nitrile of 1,3,6- hexane three, pimelic dinitrile.
A kind of 6. lithium-ion battery electrolytes according to claim 1, it is characterised in that：The additive also includes low-resistance
Anti- additive E, the Low ESR additive E are vinylene carbonate VC, propylene sulfite PS, butylene sulfite BS, sulphur
At least one of sour ethyl DTD, the addition of the Low ESR additive E account for the 0.1~1.5% of electrolyte gross mass.
A kind of 7. lithium-ion battery electrolytes according to claim 1, it is characterised in that：The Non-aqueous Organic Solvents are
Dimethyl carbonate DMC, diethyl carbonate DEC, methyl ethyl carbonate EMC, propene carbonate PC, ethylene carbonate EC and carbonic acid first third
The two or more mixtures mixed in any proportion in ester MPC；The Non-aqueous Organic Solvents account for electrolyte gross mass
65%~85%.
A kind of 8. lithium-ion battery electrolytes according to claim 1, it is characterised in that：The lithium salts is hexafluorophosphoric acid
Lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine sulfimide lithiums, LiBF4, double trifluoromethanesulfonimide lithiums
At least one of；The lithium salts accounts for the 10%~20% of electrolyte gross mass.
9. a kind of lithium ion battery, including wind and form in the same direction after being stacked gradually by positive plate, barrier film and negative plate
Core and electrolyte, it is characterised in that：The electrolyte is the lithium ion battery battery described in any one of claim 1~8
Solve liquid.
A kind of 10. lithium ion battery according to claim 9, it is characterised in that：The positive electrode of the positive plate includes
At least one of cobalt acid lithium, LiMn2O4, nickel ion doped, nickle cobalt lithium manganate, and it is 0.1~1% also to include weight/mass percentage composition
Lithium carbonate.
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