CN107887647A - A kind of 5V high voltages electrolyte for lithium secondary batteries and the lithium secondary battery containing the electrolyte - Google Patents
A kind of 5V high voltages electrolyte for lithium secondary batteries and the lithium secondary battery containing the electrolyte Download PDFInfo
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- CN107887647A CN107887647A CN201711012849.0A CN201711012849A CN107887647A CN 107887647 A CN107887647 A CN 107887647A CN 201711012849 A CN201711012849 A CN 201711012849A CN 107887647 A CN107887647 A CN 107887647A
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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
- H01M10/42—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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- 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 discloses a kind of 5V high voltages electrolyte for lithium secondary batteries, including cathode film formation additive, electrolyte stabilizer, electrolyte lithium salt and non-aqueous organic solvent, it is characterised in that described electrolyte also includes positive pole film for additive and size；Described positive pole film for additive is made up of phenyl anhydrides material composition, described size one or both of glyceryl tristearate, glycerol trioleate；It is an object of the invention to provide a kind of 5V high voltages electrolyte for lithium secondary batteries, the advantage of the electrolyte is that it is possible to be effectively improved the high-temperature storage performance and cycle performance of 5V high voltage lithium secondary batteries.Meanwhile the invention also discloses the 5V high voltage lithium secondary batteries using the electrolyte.
Description
Technical field
The present invention relates to lithium secondary cell electrolyte field, is electrolysed more particularly to a kind of 5V high voltages secondary lithium batteries
Liquid and preparation method thereof and lithium secondary battery.
Background technology
Lithium secondary battery is widely used because having the advantages that energy density height, good cycle.5V high-voltage anodes
Material has bigger potentiality to be exploited and market prospects because it has higher energy density.Such as led in batteries of electric automobile
Domain, high-voltage anode material mean to connect less cell, smaller total battery volume, lighter battery quality and more
High energy.
But there is problems with existing 5V high-voltage anode materials lithium secondary battery：High-temperature behavior and cycle performance
Difference.
At present, solve the problems, such as that 5V high voltage lithium secondary batteries exist and there are some researchs in terms of electrolyte.Such as
High voltage electrolytes and lithium secondary battery disclosed in patent CN201510247185.0, it use two nitrile compounds and mononitrile
The mixture of class compound is as electrolyte solvent.A kind of lithium secondary cell electrolyte as disclosed in patent CN201010291454
And the lithium secondary battery containing the electrolyte, it use the mixture of fluoro dintrile, imidazolium compounds and fluoro sulfoxide as
The solvent of electrolyte.As patent CN201310528328 discloses a kind of electrolyte for lithium secondary batteries, fluoro silicon is it used
Solvent of the alkane as electrolyte.But these patents all only have some improvement to cycle performance of battery.Therefore, how from electrolysis
It is that those skilled in the art need to examine to be set out in terms of liquid while improve the high-temperature behavior of high voltage lithium secondary battery and cycle performance
The problem of worry.
The content of the invention
Based on this, it is an object of the invention to provide a kind of 5V high voltages electrolyte for lithium secondary batteries, solves 5V high voltages
The high temperature and poor circulation problem of lithium secondary battery.
Specific technical scheme is as follows：A kind of 5V high voltages electrolyte for lithium secondary batteries, including cathode film formation additive,
Electrolyte stabilizer, electrolyte lithium salt and non-aqueous organic solvent, described electrolyte also include positive pole film for additive and infiltration
Agent.
For described positive pole film for additive by phenyl anhydrides material composition, it accounts for the 1~3% of electrolyte gross mass, institute
One or more of the phenyl anhydrides material stated in following structural formula：
Wherein, R1、R2、R3、R4And R5Independently selected from hydrogen or methyl.
Described size is made up of one or both of glyceryl tristearate, glycerol trioleate, and it accounts for electrolysis
The 0.1~0.5% of liquid gross mass.
Described cathode film formation additive is by fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate
One or more composition, it accounts for the 1~15% of electrolyte gross mass.
Described electrolyte stabilizer is made up of one or both of triphenyl phosphite, dicyclohexylcarbodiimide,
It accounts for the 0.05~0.1% of electrolyte gross mass.
Described electrolyte lithium salt is appointing in lithium hexafluoro phosphate, lithium perchlorate, double fluorine sulfimide lithiums, hexafluoroarsenate lithium
One is a kind of, and it accounts for the 10-17% of electrolyte gross mass.
Described non-aqueous organic solvent is by ethylmethane sulfonate (EMS), sulfolane (TMS), positive fourth sulfone (BS), ethylene carbonate
Ester (EC), propene carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), ethyl acetate (EA), acetic acid
A variety of compositions in propyl ester (PA), ethyl propionate (EP), it accounts for the 65-80% of electrolyte gross mass.
Meanwhile the present invention also aims to, there is provided a kind of 5V high voltages lithium secondary battery, including positive electrode are nickel manganese
One kind in sour lithium, cobalt phosphate lithium, lithium manganese phosphate, negative material is lithium titanate, one kind in graphite, silicon-carbon, described lithium two
The electrolyte of primary cell is any electrolyte as described above.
The principle and advantage of the present invention is as follows：
The present invention is combined using phenyl acid anhydrides with size, and phenyl anhydrides additive can be formed on positive electrode surface
Diaphragm, positive electrode is protected not to be damaged in high temperature storage and cyclic process；Size can be such that electrolyte fully soaks
Pole piece, so as to improve cycle performance.In addition, stabilizer and cathode film formation agent are also added with electrolyte of the present invention, the addition of four classes
Agent interacts so that electrolyte property is more excellent.Therefore, the high temperature storage of lithium secondary battery can be improved using the electrolyte
Energy and cycle performance.
Brief description of the drawings
Fig. 1 is the normal temperature circulation experimental results figure of embodiment 1 and comparative example 1；
Fig. 2 is the normal temperature circulation experimental results figure of embodiment 2 and comparative example 2；
Fig. 3 is the normal temperature circulation experimental results figure of embodiment 3 and comparative example 3；
Fig. 4 is the normal temperature circulation experimental results figure of embodiment 4 and comparative example 4；
Fig. 5 is the normal temperature circulation experimental results figure of embodiment 5 and comparative example 5；
Fig. 6 is the normal temperature circulation experimental results figure of embodiment 6 and comparative example 6；
Fig. 7 is the normal temperature circulation experimental results figure of embodiment 7 and comparative example 7；
Fig. 8 is the normal temperature circulation experimental results figure of embodiment 8 and comparative example 8；
Fig. 9 is the normal temperature circulation experimental results figure of embodiment 9 and comparative example 9；
Figure 10 is the normal temperature circulation experimental results figure of embodiment 1 and comparative example 10,11,12；
Embodiment
The application is further elaborated by the following examples.
Embodiment 1
Battery makes：
It is prepared by positive pole：Positive electrode matches：Nickel ion doped, acetylene black (conductive agent), polyvinylidene fluoride (PVDF, glue
Tie agent) mass ratio be 95:2.5:2.5.PVDF is added in N- methyl-pyrrolidons, high-speed stirred is uniform, adds into solution
Enter acetylene black, stir, then add nickel ion doped and stir to form anode sizing agent, anode sizing agent is coated in aluminium foil
On, positive plate is toasted, is compacted, cut-parts, welding electrode ear.
It is prepared by negative pole：Negative material proportioning is Si-C composite material, acetylene black, carboxymethyl cellulose (CMC), the rubber of fourth third
(SBR), mass ratio 95:1.0:1.5:2.5.CMC is added to the water, high-speed stirred is completely dissolved it, then adds acetylene
It is black, continue to be stirred until homogeneous, continuously add Si-C composite material (Si contents are 3%) powder, stir after disperseing, add
SBR, uniform cathode size is dispersed into, by cathode size coated on copper foil, negative plate is toasted, is compacted, cut-parts, weldering
Lug.
It is prepared by electrolyte：In the glove box full of argon gas (moisture ＜ 10ppm, oxygen ＜ 1ppm), take that to account for electrolyte total
TMS, EC, DMC, EMC mixed liquor (mass ratio 1 of quality 78.6%:2:5:3) additive fluorine, is added into mixed liquor successively
For ethylene carbonate, vinylene carbonate, vinylethylene carbonate, phthalic anhydride, pyromellitic dianhydride, phosphorous triphenyl phosphate
Ester, dicyclohexylcarbodiimide, glyceryl tristearate, glycerol trioleate, addition account for electrolyte gross mass successively
7.00%th, 1.00%, 1.00%, 1.00%, 1.00%, 0.05%, 0.05%, 0.10%, 0.20%, in most backward mixed liquor
The lithium hexafluoro phosphate for accounting for electrolyte gross mass 10.00% is added, the electrolyte A1 of embodiment 1 is obtained after stirring.
The preparation of battery：The positive plate that will be obtained, negative plate, battery core is wound into polyethylene diagrams, loads cylindrical battery
In shell, above-mentioned electrolyte is injected in battery, 18650 type cylindrical batteries are made in sealing.Obtain the secondary electricity of sample lithium of embodiment 1
Pond S1.
Embodiment 2
Electrolyte A2 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive added is fluoro
Ethylene carbonate, phthalic anhydride, triphenyl phosphite, glyceryl tristearate, addition account for electrolyte gross mass successively
15.00%, 2.00%, 0.10%, 0.50%, the hexafluoro for accounting for electrolyte gross mass 17.00% is added in most backward mixed liquor
Lithium phosphate.Remaining component is non-aqueous organic solvent, non-aqueous organic solvent TMS, EC, DMC, EMC mixed liquor (mass ratio 1:
2:5:3) the 65.40% of electrolyte gross mass, is accounted for.
Lithium secondary battery S2 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For nickel ion doped, negative material is graphite material；Remaining is the same as embodiment 1.
Embodiment 3
Electrolyte A3 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive added is carbonic acid
Vinylene, vinylethylene carbonate, 3- methyl-benzene -1,2,4,5- tetrabasic carboxylic acid -1,2,4,5- dianhydrides, dicyclohexyl carbon two are sub-
Amine, glycerol trioleate, addition account for 0.50%, 0.50%, 3.00%, 0.10%, the 0.50% of electrolyte gross mass successively,
The lithium hexafluoro phosphate for accounting for electrolyte gross mass 14.40% is added in most backward mixed liquor.Remaining component is non-aqueous organic solvent,
Non-aqueous organic solvent is TMS, EC, DMC, EMC mixed liquor (mass ratio 1:2:5:3) the 81.0% of electrolyte gross mass, is accounted for.
Lithium secondary battery S3 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For nickel ion doped, negative material is lithium titanate material；Remaining is the same as embodiment 1.
Embodiment 4
Electrolyte A4 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive added is fluoro
Ethylene carbonate, mellitic acid acid anhydride, triphenyl phosphite, glycerol trioleate, addition account for electrolyte gross mass successively
10.00%th, 1.00%, 0.08%, 0.30%, the perchloric acid for accounting for electrolyte gross mass 15.00% is added in most backward mixed liquor
Lithium.Remaining component is non-aqueous organic solvent, non-aqueous organic solvent TMS, EC, DMC, EMC mixed liquor (mass ratio 1:2:5:
3) the 73.62% of electrolyte gross mass, is accounted for.
Lithium secondary battery S4 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For cobalt phosphate lithium, negative material is Si-C composite material (Si contents are 3%)；Remaining is the same as embodiment 1.
Embodiment 5
Electrolyte A5 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive added is fluoro
Ethylene carbonate, vinylethylene carbonate, phthalic anhydride, triphenyl phosphite, glyceryl tristearate, addition is successively
3.00%, 0.50%, 3.00%, 0.07%, the 0.50% of electrolyte gross mass is accounted for, is added in most backward mixed liquor and accounts for electrolyte
Double fluorine sulfimide lithiums of gross mass 13.50%.Remaining component is non-aqueous organic solvent, non-aqueous organic solvent TMS, EC,
DMC, EMC mixed liquor (mass ratio 1:2:5:3) the 79.43% of electrolyte gross mass, is accounted for.
Lithium secondary battery S5 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For cobalt phosphate lithium, negative material is graphite material；Remaining is the same as embodiment 1.
Embodiment 6
Electrolyte A6 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive added is fluoro
Ethylene carbonate, pyromellitic dianhydride, dicyclohexylcarbodiimide, glycerol trioleate, addition account for the total matter of electrolyte successively
12.00%, 2.50%, 0.05%, the 0.50% of amount, add in most backward mixed liquor and account for the six of electrolyte gross mass 16.00%
Fluorine arsenic acid lithium.Remaining component is non-aqueous organic solvent, and (mass ratio is non-aqueous organic solvent TMS, EC, DMC, EMC mixed liquor
1:2:5:3) the 68.95% of electrolyte gross mass, is accounted for.
Lithium secondary battery S6 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For cobalt phosphate lithium, negative material is lithium titanate material；Remaining is the same as embodiment 1.
Embodiment 7
Electrolyte A7 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive added is fluoro
Ethylene carbonate, vinylene carbonate, pyromellitic dianhydride, dicyclohexylcarbodiimide, glycerol trioleate, addition is successively
8.00%, 1.00%, 3.00%, 0.10%, the 0.50% of electrolyte gross mass is accounted for, is added in most backward mixed liquor and accounts for electrolyte
Double fluorine sulfimide lithiums of gross mass 14.40%.Remaining component is non-aqueous organic solvent, non-aqueous organic solvent EMS, EC,
PC, DMC, DEC, PA mixed liquor (mass ratio 1:2:1:4:1:1)；Account for the 73.0% of electrolyte gross mass.
Lithium secondary battery S7 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For lithium manganese phosphate, negative material is Si-C composite material (Si contents are 3%)；Remaining is the same as embodiment 1.
Embodiment 8
Electrolyte A8 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive fluoro carbon added
Vinyl acetate, vinylene carbonate, mellitic acid acid anhydride, triphenyl phosphite, dicyclohexylcarbodiimide, glycerol trioleate,
Addition accounts for 8.00%, 1.00%, 2.00%, 0.05%, 0.05%, the 0.10% of electrolyte gross mass successively, most backward mixed
Close the lithium perchlorate for being added in liquid and accounting for electrolyte gross mass 16.00%.Remaining component is non-aqueous organic solvent, non-aqueous organic molten
Agent is BS, EC, DMC, EA mixed liquor (mass ratio 1:2:6:1) the 72.8% of electrolyte gross mass, is accounted for.
Lithium secondary battery S8 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For lithium manganese phosphate, negative material is graphite material；Remaining is the same as embodiment 1.
Embodiment 9
Electrolyte A9 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive added is fluoro
Ethylene carbonate, pyromellitic dianhydride, triphenyl phosphite, glyceryl tristearate, addition account for electrolyte gross mass successively
12.00%, 3.00%, 0.10%, 0.50%, the hexafluoro for accounting for electrolyte gross mass 10.00% is added in most backward mixed liquor
Lithium phosphate.Remaining component is non-aqueous organic solvent, non-aqueous organic solvent BS, EC, DMC, EP, EMC liquid (mass ratio 1:1:
5:2:1) the 74.4% of electrolyte gross mass, is accounted for.
Lithium secondary battery S9 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For lithium manganese phosphate, negative material is lithium titanate material；Remaining is the same as embodiment 1.
Comparative example 1
Electrolyte DA1 is prepared using the electrolyte method of embodiment 1, the difference is that the additive added is phthalic acid
Acid anhydride, pyromellitic dianhydride, triphenyl phosphite, dicyclohexylcarbodiimide, glyceryl tristearate, glycerol trioleate, add
Enter amount accounts for electrolyte gross mass successively 1.00%, 1.00%, 0.05%, 0.05%, 0.10%, 0.20%, most backward mixing
The lithium hexafluoro phosphate for accounting for electrolyte gross mass 10.00% is added in liquid.Remaining component is non-aqueous organic solvent, non-aqueous organic molten
Agent is TMS, EC, DMC, EMC mixed liquor (mass ratio 1:2:5:3).
Lithium secondary battery DS1 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.
Comparative example 2
Electrolyte DA2 is prepared using the electrolyte method of embodiment 1, the difference is that the additive added is phthalic acid
Acid anhydride, triphenyl phosphite, glyceryl tristearate, addition account for successively electrolyte gross mass 2.00%, 0.10%,
0.50%, the lithium hexafluoro phosphate for accounting for electrolyte gross mass 17.00% is added in most backward mixed liquor.Remaining component has to be non-aqueous
Solvent, non-aqueous organic solvent TMS, EC, DMC, EMC mixed liquor (mass ratio 1:2:5:3).
Lithium secondary battery DS2 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For nickel ion doped, negative material is graphite material；Remaining is the same as embodiment 1.
Comparative example 3
Electrolyte DA3 is prepared using the electrolyte method of embodiment 1, the difference is that the additive added is vinylene carbonate
Ester, vinylethylene carbonate, dicyclohexylcarbodiimide, glycerol trioleate, addition account for electrolyte gross mass successively
0.50%th, 0.50%, 0.10%, 0.50%, the hexafluorophosphoric acid for accounting for electrolyte gross mass 14.40% is added in most backward mixed liquor
Lithium.Remaining component is non-aqueous organic solvent, non-aqueous organic solvent TMS, EC, DMC, EMC mixed liquor (mass ratio 1:2:5:
3)。
Lithium secondary battery DS3 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For nickel ion doped, negative material is silicon-carbon lithium titanate material；Remaining is the same as embodiment 1.
Comparative example 4
Electrolyte DA4 is prepared using the electrolyte method of embodiment 1, the difference is that the additive added is fluoro ethylene carbonate
Ester, triphenyl phosphite, glycerol trioleate, addition account for 10.00%, 0.08%, the 0.30% of electrolyte gross mass successively,
The lithium perchlorate for accounting for electrolyte gross mass 15.00% is added in most backward mixed liquor.Remaining component is non-aqueous organic solvent, non-
Water organic solvent is TMS, EC, DMC, EMC mixed liquor (mass ratio 1:2:5:3).
Lithium secondary battery DS4 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For cobalt phosphate lithium, negative material is Si-C composite material (Si contents are 3%)；Remaining is the same as embodiment 1.
Comparative example 5
Electrolyte DA5 is prepared using the electrolyte method of embodiment 1, the difference is that the additive added is fluoro ethylene carbonate
Ester, vinylethylene carbonate, triphenyl phosphite, glyceryl tristearate, addition account for electrolyte gross mass successively
3.00%th, 0.50%, 0.070%, 0.50%, the double fluorine sulphurs for accounting for electrolyte gross mass 13.50% are added in most backward mixed liquor
Imide li.Remaining component is non-aqueous organic solvent, and (mass ratio is non-aqueous organic solvent TMS, EC, DMC, EMC mixed liquor
1:2:5:3)。
Lithium secondary battery DS5 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For cobalt phosphate lithium, negative material is graphite material；Remaining is the same as embodiment 1.
Comparative example 6
Electrolyte DA6 is prepared using the electrolyte method of embodiment 1, the difference is that the additive added is fluoro ethylene carbonate
Ester, pyromellitic dianhydride, glycerol trioleate, addition account for 12.00%, 2.50%, the 0.50% of electrolyte gross mass successively,
The hexafluoroarsenate lithium for accounting for electrolyte gross mass 16.00% is added in most backward mixed liquor.Remaining component is non-aqueous organic solvent,
Non-aqueous organic solvent is TMS, EC, DMC, EMC mixed liquor (mass ratio 1:2:5:3).
Lithium secondary battery DS6 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For cobalt phosphate lithium, negative material is lithium titanate material；Remaining is the same as embodiment 1.
Comparative example 7
Electrolyte DA7 is prepared using the electrolyte method of embodiment 1, the difference is that the additive added is fluoro ethylene carbonate
Ester, vinylene carbonate, pyromellitic dianhydride, glycerol trioleate, addition account for successively electrolyte gross mass 8.00%,
1.00%th, 3.00%, 0.50%, the double fluorine sulfimide lithiums for accounting for electrolyte gross mass 14.40% are added in most backward mixed liquor.
Remaining component is non-aqueous organic solvent, non-aqueous organic solvent EMS, EC, PC, DMC, DEC, PA mixed liquor (mass ratio 1:
2:1:4:1:1)。
Lithium secondary battery DS7 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For lithium manganese phosphate, negative material is Si-C composite material (Si contents are 3%)；Remaining is the same as embodiment 1.
Comparative example 8
Electrolyte DA8 is prepared using the electrolyte method of embodiment 1, the difference is that the additive added is fluoro ethylene carbonate
Ester, vinylene carbonate, mellitic acid acid anhydride, triphenyl phosphite, dicyclohexylcarbodiimide, it is total that addition accounts for electrolyte successively
8.00%, 1.00%, 2.00%, 0.05%, the 0.05% of quality, add in most backward mixed liquor and account for electrolyte gross mass
16.00% lithium perchlorate.Remaining component is non-aqueous organic solvent, non-aqueous organic solvent BS, EC, DMC, EA mixed liquor
(mass ratio 1:2:6:1).
Lithium secondary battery DS8 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For lithium manganese phosphate, negative material is graphite material；Remaining is the same as embodiment 1.
Comparative example 9
Electrolyte DA9 is prepared using the electrolyte method of embodiment 1, the difference is that the additive added is fluoro ethylene carbonate
Ester, pyromellitic dianhydride, triphenyl phosphite, addition account for 12.00%, 3.00%, the 0.10% of electrolyte gross mass successively,
The lithium hexafluoro phosphate for accounting for electrolyte gross mass 10.00% is added in most backward mixed liquor.Remaining component is non-aqueous organic solvent,
Non-aqueous organic solvent is BS, EC, DMC, EP, EMC liquid (mass ratio 1:1:5:2:1).
Lithium secondary battery DS9 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.The difference is that positive electrode
For lithium manganese phosphate, negative material is lithium titanate material；Remaining is the same as embodiment 1.
Comparative example 10
Electrolyte DA10 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive added is fluorine
For ethylene carbonate, vinylene carbonate, vinylethylene carbonate, phthalic anhydride, pyromellitic dianhydride, phosphoric acid triphen
Ester, pyridine, glyceryl tristearate, glycerol trioleate, addition account for successively electrolyte gross mass 1.00%, 7.00%,
1.00%th, 1.00%, 1.00%, 1.00%, 0.05%, 0.05%, 0.10%, 0.20%, add in most backward mixed liquor and account for
The lithium hexafluoro phosphate of electrolyte gross mass 10.00%.Remaining component is non-aqueous organic solvent, matches same embodiment 1.Wherein,
Triphenyl phosphate, pyridine use as stabilizer.
Lithium secondary battery DS10 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.
Comparative example 11
Electrolyte DA11 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive added is fluorine
For ethylene carbonate, vinylene carbonate, vinylethylene carbonate, phthalic anhydride, pyromellitic dianhydride, phosphorous triphenyl phosphate
Ester, dicyclohexylcarbodiimide, glyceryl triacetate, addition account for successively electrolyte gross mass 7.00%, 1.00%,
1.00%th, 1.00%, 1.00%, 0.05%, 0.05%, 0.30%, add in most backward mixed liquor and account for electrolyte gross mass
10.00% lithium hexafluoro phosphate.Remaining component is non-aqueous organic solvent, matches same embodiment 1.Wherein, glyceryl triacetate
As size.
Lithium secondary battery DS11 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.
Comparative example 12
Electrolyte DA11 is prepared using the preparation method of the electrolyte of embodiment 1, the difference is that the additive added is fluorine
For ethylene carbonate, vinylene carbonate, vinylethylene carbonate, phthalic anhydride, pyromellitic dianhydride, phosphorous triphenyl phosphate
Ester, dicyclohexylcarbodiimide, glyceryl tripropanoate, addition account for successively electrolyte gross mass 7.00%, 1.00%,
1.00%th, 1.00%, 1.00%, 0.05%, 0.05%, 0.30%, add in most backward mixed liquor and account for electrolyte gross mass
10.00% lithium hexafluoro phosphate.Remaining component is non-aqueous organic solvent, matches same embodiment 1.Wherein, glyceryl tripropanoate
As size.
Lithium secondary battery DS12 is prepared according to the method for embodiment 1 using above-mentioned electrolyte.
Test experiments
All embodiments 1~9 and the gained battery of all comparative examples 1~12 are tested as follows：
Normal temperature circulation is tested：It is lithium titanate material battery at room temperature with 0.5C/0.5C by comparative example and embodiment negative pole
Charge-discharge magnification carry out charge and discharge cycles test in the range of 1.5~3.5V, negative pole be graphite and silicon-carbon battery at room temperature
Charge and discharge cycles test is carried out in the range of 3~5V with 0.5C/0.5C charge-discharge magnification, record cyclic discharge capacity and divided by
Circulate for 1st time discharge capacity produces capability retention, record result such as Fig. 1-10.
High temperature storage is tested：It is that lithium titanate material battery is first at room temperature with 0.5C/ by the negative pole of comparative example and embodiment
0.5C charge-discharge magnification charges to 3.5V in 1.5~3.5V discharge and recharges 3 times, then with 0.5C, records the 3rd discharge capacity.Will
Battery is placed in 60 DEG C of baking ovens and stored 7 days, treats that battery is cooled to room temperature, then at room temperature with 0.5C/0.5C discharge and recharge times
Rate is in 1.5~3.5V discharge and recharges 3 times, the 1st discharge capacity of record and the 3rd discharge capacity.With the 1st discharge capacity after storage
Divided by the 3rd discharge capacity produces capability retention before storage, put with the 3rd time before the 3rd discharge capacity after storage divided by storage
Capacitance produces capacity restoration rate, as a result record such as table 1.
It is that graphite and silicon-carbon battery are first at room temperature with 0.5C/0.5C discharge and recharge times by the negative pole of comparative example and embodiment
Rate charges to 5V in 3~5V discharge and recharges 3 times, then with 0.5C, records the 3rd discharge capacity.Battery is placed in 60 DEG C of baking ovens
Storage 7 days, treat that battery is cooled to room temperature, then at room temperature with 0.5C/0.5C charge-discharge magnification in 3~5V discharge and recharges 3 times, note
Record the 1st discharge capacity and the 3rd discharge capacity.It is with the 3rd discharge capacity before the 1st discharge capacity after storage divided by storage
Capability retention is obtained, capacity restoration rate is produced with the 3rd discharge capacity before the 3rd discharge capacity after storage divided by storage, as a result
Record such as table 1.
Table 1：Capacitance of lithium secondary battery conservation rate, capacity restoration rate test result
Shown with reference to Fig. 1, Fig. 2 and the result of table 1：S1 and SD1 contrast, S2 and SD2 are contrasted, with the addition of in electrolyte negative pole into
Film additive, cycle performance of battery and high-temperature storage performance significantly improve, and illustrate fluorinated ethylene carbonate, vinylene carbonate
Ester, vinylethylene carbonate can be with negative material surface filming, improving battery performance.
Shown with reference to Fig. 3, Fig. 4, Fig. 5 and the result of table 1：S3 and DS3 contrasts, S4 and SD4 contrasts, S5 and SD5 are contrasted, electrolysis
Positive pole film for additive phenyl anhydride compound is with the addition of in liquid, cycle performance of battery and high-temperature storage performance are significantly improved, said
Bright phenyl acid anhydrides can reduce being contacted with the direct of positive pole for electrolyte, reduce the oxygen of electrolyte in positive electrode surface filming
Change decomposition reaction, improve battery performance.
Shown with reference to Fig. 6, Fig. 7 and the result of table 1：S6 and SD6 contrasts, S7 and SD7 are contrasted, and stabilizer is with the addition of in electrolyte
Triphenyl phosphite, dicyclohexylcarbodiimide, cycle performance and it is high it is gentle be improved significantly, illustrate triphenyl phosphite,
Dicyclohexylcarbodiimide, the generation side reaction for suppressing electrolyte are decomposed, and improve battery performance.
Shown with reference to Fig. 8, Fig. 9 and the result of table 1：S8 and SD8 contrasts, S9 and SD9 are contrasted, and size is with the addition of in electrolyte
Glyceryl tristearate, glycerol trioleate, cycle performance are obviously improved, and illustrate glyceryl tristearate, glycerol trioleate,
Improve wellability of the electrolyte to pole piece, improve battery performance.
Shown with reference to Figure 10 and the result of table 1：S1 and DS10 contrasts, understand triphenyl phosphite, dicyclohexylcarbodiimide
It is better as electrolyte stabilizer effect；S1 contrasts with DS11, DS12, it is known that glyceryl tristearate, glycerol trioleate
It is better as size effect；
By above-mentioned analysis it is known that thering is phenyl acid anhydrides to be combined with size in the electrolyte of the present invention, phenyl acid anhydrides
Class additive can form diaphragm on positive electrode surface, protect positive electrode in high temperature storage and cyclic process not by broken
It is bad；Size can make electrolyte fully soak pole piece, so as to improve cycle performance.In addition, in electrolyte also have negative pole into
Film additive, stabilizer.Mutually cooperateed between this four classes additive component, be an organic whole, it more can effectively be carried
The cycle performance and high-temperature behavior of high 5V high voltages lithium secondary battery.
Embodiment described above only expresses embodiments of the present invention, and its description is more specific and detailed, but can not
Therefore it is construed as limiting the scope of the patent.It should be pointed out that for the person of ordinary skill of the art,
On the premise of not departing from present inventive concept, various modifications and improvements can be made, these belong to protection scope of the present invention.
Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (8)
1. a kind of 5V high voltages electrolyte for lithium secondary batteries, including cathode film formation additive, electrolyte stabilizer, electrolyte lithium
Salt and non-aqueous organic solvent, it is characterised in that described electrolyte also includes positive pole film for additive and size.
2. 5V high voltages electrolyte for lithium secondary batteries according to claim 1, it is characterised in that described positive pole film forming
Additive is by phenyl anhydrides material composition, and it accounts for the 1~3% of electrolyte gross mass, and described phenyl anhydrides material is selected from
One or more in following structural formula：
Wherein, R1、R2、R3、R4And R5Independently selected from hydrogen or methyl.
3. 5V high voltages electrolyte for lithium secondary batteries according to claim 1, it is characterised in that described size by
One or both of glyceryl tristearate, glycerol trioleate form, and it accounts for the 0.1~0.5% of electrolyte gross mass.
4. 5V high voltages electrolyte for lithium secondary batteries according to claim 1, it is characterised in that described cathode film formation
Additive is made up of the one or more in fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, and it accounts for electrolysis
The 1~15% of liquid gross mass.
5. 5V high voltages electrolyte for lithium secondary batteries according to claim 1, it is characterised in that described electrolyte is steady
Determine agent to be made up of one or both of triphenyl phosphite, dicyclohexylcarbodiimide, it accounts for the 0.01 of electrolyte gross mass
~0.1%.
6. 5V high voltages electrolyte for lithium secondary batteries according to claim 1, it is characterised in that described electrolyte lithium
Salt is any in lithium hexafluoro phosphate, lithium perchlorate, double fluorine sulfimide lithiums, hexafluoroarsenate lithium, and it accounts for the total matter of electrolyte
The 10-17% of amount.
7. 5V high voltages electrolyte for lithium secondary batteries according to claim 1, it is characterised in that described is non-aqueous organic
Solvent by ethylmethane sulfonate (EMS), sulfolane (TMS), positive fourth sulfone (BS), ethylene carbonate (EC), propene carbonate (PC),
It is more in dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), ethyl acetate (EA), propyl acetate (PA), ethyl propionate (EP)
Kind composition, it accounts for the 65-80% of electrolyte gross mass.
8. a kind of 5V high voltages lithium secondary battery, including positive electrode be in nickel ion doped, cobalt phosphate lithium, lithium manganese phosphate one
Kind, negative material is one kind in lithium titanate, graphite, silicon-carbon, it is characterised in that the electrolyte of described lithium secondary battery is such as
Any electrolyte described in claim 1-7.
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| CN116632353A (en) * | 2023-07-17 | 2023-08-22 | 江苏兴杰固邦能源科技有限公司 | Lithium ion battery electrolyte capable of inhibiting formation and growth of lithium dendrite and lithium ion battery |
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