CN107887647B - Electrolyte for 5V high-voltage lithium secondary battery and lithium secondary battery containing electrolyte - Google Patents
Electrolyte for 5V high-voltage lithium secondary battery and lithium secondary battery containing electrolyte Download PDFInfo
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- CN107887647B CN107887647B CN201711012849.0A CN201711012849A CN107887647B CN 107887647 B CN107887647 B CN 107887647B CN 201711012849 A CN201711012849 A CN 201711012849A CN 107887647 B CN107887647 B CN 107887647B
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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 an electrolyte for a 5V high-voltage lithium secondary battery, which comprises a negative electrode film-forming additive, an electrolyte stabilizer, electrolyte lithium salt and a non-aqueous organic solvent, and is characterized in that the electrolyte also comprises a positive electrode film-forming additive and a wetting agent; the positive film-forming additive consists of phenyl anhydride substances, and the impregnating compound consists of one or two of tristearin and glycerol trioleate; an object of the present invention is to provide an electrolyte for a 5V high voltage lithium secondary battery, which is advantageous in that the high temperature storage performance and cycle performance of the 5V high voltage lithium secondary battery can be effectively improved. Meanwhile, the invention also discloses a 5V high-voltage lithium secondary battery adopting the electrolyte.
Description
Technical Field
The invention relates to the field of electrolyte of lithium secondary batteries, in particular to electrolyte for a 5V high-voltage lithium secondary battery, a preparation method of the electrolyte and the lithium secondary battery.
Background
Lithium secondary batteries are widely used because of their advantages such as high energy density and good cycle performance. The 5V high-voltage positive electrode material has higher energy density, and has greater development potential and market prospect. In the field of batteries for electric vehicles, for example, high voltage positive electrode materials mean fewer individual batteries connected in series, smaller total battery volume, lighter battery mass and higher energy.
However, the conventional 5V high-voltage positive electrode material lithium secondary battery has the following problems: the high temperature performance and the cycle performance are poor.
Currently, there have been some studies to solve the problems of the 5V high voltage lithium secondary battery in terms of an electrolyte. For example, patent CN201510247185.0 discloses a high voltage electrolyte and a lithium secondary battery using a mixture of dinitrile compounds and mononitrile compounds as an electrolyte solvent. For example, patent CN201010291454 discloses an electrolyte for a lithium secondary battery and a lithium secondary battery containing the same, which uses a mixture of fluorinated dinitrile, imidazole compound and fluorinated sulfoxide as a solvent of the electrolyte. For example, patent CN201310528328 discloses an electrolyte for a lithium secondary battery, which uses fluorosilane as a solvent of the electrolyte. However, these patents only provide some improvement in the cycling performance of the battery. Therefore, how to improve both the high-temperature performance and the cycle performance of the high-voltage lithium secondary battery from the viewpoint of the electrolyte is a matter of consideration for those skilled in the art.
Disclosure of Invention
Based on this, an object of the present invention is to provide an electrolyte for a 5V high voltage lithium secondary battery, which solves the problems of high temperature and poor cycle performance of the 5V high voltage lithium secondary battery.
The specific technical scheme is as follows: the electrolyte for the 5V high-voltage lithium secondary battery comprises a negative electrode film-forming additive, an electrolyte stabilizer, electrolyte lithium salt and a non-aqueous organic solvent, and further comprises a positive electrode film-forming additive and a wetting agent.
The positive film-forming additive consists of phenyl anhydride substances which account for 1-3% of the total mass of the electrolyte, and the phenyl anhydride substances are selected from one or more of the following structural formulas:
wherein R is1、R2、R3、R4And R5Independently selected from hydrogen or methyl.
The impregnating compound consists of one or two of glyceryl tristearate and glycerol trioleate, and accounts for 0.1-0.5% of the total mass of the electrolyte.
The negative electrode film forming additive is composed of one or more of fluoroethylene carbonate, vinylene carbonate and ethylene carbonate, and accounts for 1-15% of the total mass of the electrolyte.
The electrolyte stabilizer is composed of one or two of triphenyl phosphite and dicyclohexyl carbodiimide, and accounts for 0.05-0.1% of the total mass of the electrolyte.
The electrolyte lithium salt is any one of lithium hexafluorophosphate, lithium perchlorate, lithium bis (fluorosulfonyl) imide and lithium hexafluoroarsenate, and accounts for 10-17% of the total mass of the electrolyte.
The non-aqueous organic solvent consists of a plurality of Ethyl Methanesulfonate (EMS), sulfolane (TMS), n-Butyl Sulfone (BS), Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), Ethyl Acetate (EA), Propyl Acetate (PA) and Ethyl Propionate (EP), and accounts for 65-80% of the total mass of the electrolyte.
Meanwhile, the invention also aims to provide a 5V high-voltage lithium secondary battery, which comprises a positive electrode material which is one of lithium nickel manganese oxide, lithium cobalt phosphate and lithium manganese phosphate, a negative electrode material which is one of lithium titanate, graphite and silicon carbon, and an electrolyte of the lithium secondary battery is any one of the above electrolytes.
The principle and advantages of the invention are as follows:
according to the invention, the phenyl anhydride and the impregnating compound are combined, and the phenyl anhydride additive can form a protective film on the surface of the anode material, so that the anode material is protected from being damaged in the high-temperature storage and circulation processes; the impregnating compound can enable the electrolyte to fully wet the pole piece, so that the cycle performance is improved. In addition, the electrolyte is also added with a stabilizer and a negative film-forming agent, and the four additives interact with each other, so that the electrolyte has better performance. Therefore, the application of the electrolyte can improve the high-temperature storage performance and the cycle performance of the lithium secondary battery.
Drawings
FIG. 1 is a graph showing the results of the test in the room temperature cycle test of example 1 and comparative example 1;
FIG. 2 is a graph showing the results of the test in the room temperature cycle test of example 2 and comparative example 2;
FIG. 3 is a graph showing the results of the test in the room temperature cycle test of example 3 and comparative example 3;
FIG. 4 is a graph showing the results of the test in the room temperature cycle test of example 4 and comparative example 4;
FIG. 5 is a graph showing the results of the test in the room temperature cycle test of example 5 and comparative example 5;
FIG. 6 is a graph showing the results of the test in the room temperature cycle test of example 6 and comparative example 6;
FIG. 7 is a graph showing the results of the room temperature cycle test of example 7 and comparative example 7;
FIG. 8 is a graph showing the results of the test in the room temperature cycle test of example 8 and comparative example 8;
FIG. 9 is a graph showing the results of the room temperature cycle test of example 9 and comparative example 9;
FIG. 10 is a graph showing the results of the room temperature cycle test of example 1 and comparative examples 10, 11 and 12;
Detailed Description
The present application is further illustrated by the following examples.
Example 1
Manufacturing a battery:
preparing a positive electrode: the anode material comprises the following components in percentage by weight: the mass ratio of the lithium nickel manganese oxide to the acetylene black (conductive agent) to the polyvinylidene fluoride (PVDF and binder) is 95:2.5: 2.5. Adding PVDF into N-methyl-pyrrolidone, stirring uniformly at a high speed, adding acetylene black into the solution, stirring uniformly, then adding lithium nickel manganese oxide, stirring uniformly to form anode slurry, coating the anode slurry on an aluminum foil, baking and compacting an anode sheet, cutting the sheet, and welding a tab.
Preparing a negative electrode: the negative electrode material comprises a silicon-carbon composite material, acetylene black, carboxymethyl cellulose (CMC) and butadiene-acrylonitrile rubber (SBR) in a mass ratio of 95:1.0:1.5: 2.5. Adding CMC into water, stirring at high speed to completely dissolve the CMC, adding acetylene black, continuously stirring until the mixture is uniform, continuously adding silicon-carbon composite material (the content of Si is 3 percent) powder, stirring and dispersing the mixture uniformly, adding SBR to disperse the mixture into uniform negative electrode slurry, coating the negative electrode slurry on copper foil, baking the negative electrode plate, compacting, cutting the plate, and welding a tab.
Preparing an electrolyte: in a glove box filled with argon (moisture < 10ppm, oxygen content < 1ppm), a mixed solution of TMS, EC, DMC and EMC (mass ratio 1:2:5:3) was taken in an amount of 78.6% of the total mass of the electrolyte, and additives of fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, phthalic anhydride, pyromellitic dianhydride, triphenyl phosphite, dicyclohexylcarbodiimide, glycerol tristearate and glycerol trioleate were sequentially added to the mixed solution in an amount of 7.00%, 1.00%, 0.05%, 0.10% and 0.20% of the total mass of the electrolyte, and finally lithium hexafluorophosphate in an amount of 10.00% of the total mass of the electrolyte was added to the mixed solution, and the mixture was uniformly stirred to obtain electrolyte a1 of example 1.
Preparing a battery: and winding the obtained positive plate, the negative plate and the polyethylene diaphragm into a battery core, filling the battery core into a cylindrical battery shell, injecting the electrolyte into the battery, and sealing to obtain the 18650 type cylindrical battery. A sample lithium secondary battery S1 of example 1 was obtained.
Example 2
Electrolyte a2 was prepared by the method for preparing the electrolyte of example 1, except that fluoroethylene carbonate, phthalic anhydride, triphenyl phosphite, and glyceryl tristearate were added in the amounts of 15.00%, 2.00%, 0.10%, and 0.50% in this order, and lithium hexafluorophosphate in the amount of 17.00% in the total mass of the electrolyte was finally added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquor of TMS, EC, DMC and EMC (the mass ratio is 1:2:5:3), and account for 65.40% of the total mass of the electrolyte.
A lithium secondary battery S2 was produced according to the method of example 1 using the above electrolyte. The difference is that the anode material is nickel lithium manganate, and the cathode material is graphite material; the rest is the same as example 1.
Example 3
Electrolyte a3 was prepared by the method for preparing the electrolyte of example 1, except that vinylene carbonate, ethylene carbonate, 3-methyl-benzene-1, 2,4, 5-tetracarboxylic acid-1, 2,4, 5-dianhydride, dicyclohexylcarbodiimide, and glycerol trioleate were added as additives in the order of 0.50%, 3.00%, 0.10%, and 0.50% by weight of the total electrolyte, and finally lithium hexafluorophosphate in the amount of 14.40% by weight of the total electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquor of TMS, EC, DMC and EMC (the mass ratio is 1:2:5:3), and account for 81.0% of the total mass of the electrolyte.
A lithium secondary battery S3 was produced according to the method of example 1 using the above electrolyte. The difference is that the anode material is lithium nickel manganese oxide, and the cathode material is lithium titanate material; the rest is the same as example 1.
Example 4
An electrolyte a4 was prepared by the method of preparing the electrolyte of example 1, except that fluoroethylene carbonate, mellitic anhydride, triphenyl phosphite, and glycerol trioleate were added in amounts of 10.00%, 1.00%, 0.08%, and 0.30% in order of the total mass of the electrolyte, and finally lithium perchlorate 15.00% in the total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquor of TMS, EC, DMC and EMC (the mass ratio is 1:2:5:3), and account for 73.62% of the total mass of the electrolyte.
A lithium secondary battery S4 was produced according to the method of example 1 using the above electrolyte. The difference is that the anode material is cobalt lithium phosphate, and the cathode material is a silicon-carbon composite material (the content of Si is 3%); the rest is the same as example 1.
Example 5
Electrolyte a5 was prepared by the method of example 1, except that fluoroethylene carbonate, ethylene carbonate, phthalic anhydride, triphenyl phosphite, and glyceryl tristearate were added in the amounts of 3.00%, 0.50%, 3.00%, 0.07%, and 0.50% in this order, and lithium bis (fluorosulfonyl) imide was added to the mixture in the amount of 13.50% in the total mass of the electrolyte. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquor of TMS, EC, DMC and EMC (the mass ratio is 1:2:5:3), and account for 79.43% of the total mass of the electrolyte.
A lithium secondary battery S5 was produced according to the method of example 1 using the above electrolyte. The difference is that the anode material is cobalt lithium phosphate, and the cathode material is graphite material; the rest is the same as example 1.
Example 6
An electrolyte a6 was prepared by the method for preparing the electrolyte of example 1, except that fluoroethylene carbonate, pyromellitic anhydride, dicyclohexylcarbodiimide, and glycerol trioleate were added in the amounts of 12.00%, 2.50%, 0.05%, and 0.50% in this order, and finally lithium hexafluoroarsenate 16.00% in the total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquor of TMS, EC, DMC and EMC (the mass ratio is 1:2:5:3), and account for 68.95% of the total mass of the electrolyte.
A lithium secondary battery S6 was produced according to the method of example 1 using the above electrolyte. The difference is that the anode material is cobalt lithium phosphate, and the cathode material is lithium titanate material; the rest is the same as example 1.
Example 7
An electrolyte a7 was prepared by the method for preparing the electrolyte of example 1, except that fluoroethylene carbonate, vinylene carbonate, pyromellitic anhydride, dicyclohexylcarbodiimide, and glycerol trioleate were added in the amounts of 8.00%, 1.00%, 3.00%, 0.10%, and 0.50% in this order, and lithium bis (fluorosulfonyl) imide was added to the mixture in the amount of 14.40% in total mass of the electrolyte. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are EMS, EC, PC, DMC, DEC and PA mixed liquor (the mass ratio is 1:2:1:4:1: 1); accounting for 73.0 percent of the total mass of the electrolyte.
A lithium secondary battery S7 was produced according to the method of example 1 using the above electrolyte. The difference is that the anode material is manganese lithium phosphate, and the cathode material is a silicon-carbon composite material (the content of Si is 3%); the rest is the same as example 1.
Example 8
An electrolyte A8 was prepared by the method for preparing the electrolyte of example 1, except that the additives fluoroethylene carbonate, vinylene carbonate, mellitic anhydride, triphenyl phosphite, dicyclohexylcarbodiimide and glycerol trioleate were added in the amounts of 8.00%, 1.00%, 2.00%, 0.05% and 0.10% in this order, and finally lithium perchlorate 16.00% in total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquor of BS, EC, DMC and EA (the mass ratio is 1:2:6:1), and account for 72.8% of the total mass of the electrolyte.
A lithium secondary battery S8 was produced according to the method of example 1 using the above electrolyte. The difference is that the anode material is manganese lithium phosphate, and the cathode material is graphite material; the rest is the same as example 1.
Example 9
Electrolyte a9 was prepared by the method of preparing the electrolyte of example 1, except that fluoroethylene carbonate, pyromellitic anhydride, triphenyl phosphite, and glyceryl tristearate were added in the amounts of 12.00%, 3.00%, 0.10%, and 0.50% in order of the total mass of the electrolyte, and finally lithium hexafluorophosphate 10.00% in the total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, wherein the non-aqueous organic solvents are BS, EC, DMC, EP and EMC liquid (the mass ratio is 1:1:5:2:1), and the non-aqueous organic solvents account for 74.4% of the total mass of the electrolyte.
A lithium secondary battery S9 was produced according to the method of example 1 using the above electrolyte. The difference is that the anode material is manganese lithium phosphate, and the cathode material is lithium titanate material; the rest is the same as example 1.
Comparative example 1
Electrolyte DA1 was prepared by the electrolyte method of example 1, except that phthalic anhydride, pyromellitic anhydride, triphenyl phosphite, dicyclohexylcarbodiimide, glycerol tristearate, and glycerol trioleate were added in the amounts of 1.00%, 0.05%, 0.10%, and 0.20% in the order of the total mass of the electrolyte, and finally lithium hexafluorophosphate in the amount of 10.00% in the total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquid of TMS, EC, DMC and EMC (mass ratio is 1:2:5: 3).
A lithium secondary battery DS1 was prepared according to the method of example 1 using the above electrolyte.
Comparative example 2
Electrolyte DA2 was prepared by the electrolyte method of example 1, except that phthalic anhydride, triphenyl phosphite, and glyceryl tristearate were added in the amounts of 2.00%, 0.10%, and 0.50% in the order of the total mass of the electrolyte, and finally lithium hexafluorophosphate in the amount of 17.00% in the total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquid of TMS, EC, DMC and EMC (mass ratio is 1:2:5: 3).
A lithium secondary battery DS2 was prepared according to the method of example 1 using the above electrolyte. The difference is that the anode material is nickel lithium manganate, and the cathode material is graphite material; the rest is the same as example 1.
Comparative example 3
Electrolyte DA3 was prepared by the electrolyte method of example 1, except that vinylene carbonate, ethylene carbonate, dicyclohexylcarbodiimide, and glycerol trioleate were added in amounts of 0.50%, 0.10%, and 0.50% in this order, and finally lithium hexafluorophosphate 14.40% in total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquid of TMS, EC, DMC and EMC (mass ratio is 1:2:5: 3).
A lithium secondary battery DS3 was prepared according to the method of example 1 using the above electrolyte. The difference is that the anode material is lithium nickel manganese oxide, and the cathode material is a silicon carbon lithium titanate material; the rest is the same as example 1.
Comparative example 4
Electrolyte DA4 was prepared by the electrolyte method of example 1, except that fluoroethylene carbonate, triphenyl phosphite, and glycerol trioleate were added in amounts of 10.00%, 0.08%, and 0.30% in order of the total mass of the electrolyte, and finally lithium perchlorate 15.00% in the total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquid of TMS, EC, DMC and EMC (mass ratio is 1:2:5: 3).
A lithium secondary battery DS4 was prepared according to the method of example 1 using the above electrolyte. The difference is that the anode material is cobalt lithium phosphate, and the cathode material is a silicon-carbon composite material (the content of Si is 3%); the rest is the same as example 1.
Comparative example 5
Electrolyte DA5 was prepared by the electrolyte method of example 1, except that fluoroethylene carbonate, ethylene carbonate, triphenyl phosphite, and glyceryl tristearate were added in amounts of 3.00%, 0.50%, 0.070%, and 0.50% in order of the total mass of the electrolyte, and lithium bis (fluorosulfonyl) imide was added to the mixture in an amount of 13.50% in the total mass of the electrolyte. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquid of TMS, EC, DMC and EMC (mass ratio is 1:2:5: 3).
A lithium secondary battery DS5 was prepared according to the method of example 1 using the above electrolyte. The difference is that the anode material is cobalt lithium phosphate, and the cathode material is graphite material; the rest is the same as example 1.
Comparative example 6
Electrolyte DA6 was prepared by the electrolyte method of example 1, except that fluoroethylene carbonate, pyromellitic anhydride, and glycerol trioleate were added in amounts of 12.00%, 2.50%, and 0.50% in the order of the total mass of the electrolyte, and lithium hexafluoroarsenate 16.00% in the total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed liquid of TMS, EC, DMC and EMC (mass ratio is 1:2:5: 3).
A lithium secondary battery DS6 was prepared according to the method of example 1 using the above electrolyte. The difference is that the anode material is cobalt lithium phosphate, and the cathode material is lithium titanate material; the rest is the same as example 1.
Comparative example 7
Electrolyte DA7 was prepared by the electrolyte method of example 1, except that fluoroethylene carbonate, vinylene carbonate, pyromellitic anhydride, and glycerol trioleate were added in amounts of 8.00%, 1.00%, 3.00%, and 0.50% in order of the total mass of the electrolyte, and finally lithium bis (fluorosulfonyl) imide was added to the mixture in an amount of 14.40% in total mass of the electrolyte. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are EMS, EC, PC, DMC, DEC and PA mixed liquor (the mass ratio is 1:2:1:4:1: 1).
A lithium secondary battery DS7 was prepared according to the method of example 1 using the above electrolyte. The difference is that the anode material is manganese lithium phosphate, and the cathode material is a silicon-carbon composite material (the content of Si is 3%); the rest is the same as example 1.
Comparative example 8
Electrolyte DA8 was prepared by the electrolyte method of example 1, except that fluoroethylene carbonate, vinylene carbonate, mellitic anhydride, triphenyl phosphite, and dicyclohexylcarbodiimide were added in the amounts of 8.00%, 1.00%, 2.00%, 0.05%, and 0.05% in this order, and lithium perchlorate 16.00% in the total mass of the electrolyte was finally added to the mixed solution. The rest components are non-aqueous organic solvents, and the non-aqueous organic solvents are mixed solution of BS, EC, DMC and EA (mass ratio is 1:2:6: 1).
A lithium secondary battery DS8 was prepared according to the method of example 1 using the above electrolyte. The difference is that the anode material is manganese lithium phosphate, and the cathode material is graphite material; the rest is the same as example 1.
Comparative example 9
Electrolyte DA9 was prepared by the electrolyte method of example 1, except that fluoroethylene carbonate, pyromellitic anhydride, and triphenyl phosphite were added in the amounts of 12.00%, 3.00%, and 0.10% in order of the total mass of the electrolyte, and finally lithium hexafluorophosphate in an amount of 10.00% in the total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, wherein the non-aqueous organic solvents are BS, EC, DMC, EP and EMC liquid (the mass ratio is 1:1:5:2: 1).
A lithium secondary battery DS9 was prepared according to the method of example 1 using the above electrolyte. The difference is that the anode material is manganese lithium phosphate, and the cathode material is lithium titanate material; the rest is the same as example 1.
Comparative example 10
An electrolyte DA10 was prepared by the method for preparing the electrolyte of example 1, except that fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, phthalic anhydride, pyromellitic anhydride, triphenyl phosphate, pyridine, glyceryl tristearate, and glyceryl trioleate were added in the amounts of 1.00%, 7.00%, 1.00%, 0.05%, 0.10%, and 0.20% in this order, and finally lithium hexafluorophosphate 10.00% in total mass of the electrolyte was added to the mixed solution. The rest components are non-aqueous organic solvents, and the mixture ratio is the same as that of the example 1. Wherein, triphenyl phosphate and pyridine are used as stabilizing agents.
A lithium secondary battery DS10 was prepared according to the method of example 1 using the above electrolyte.
Comparative example 11
An electrolyte DA11 was prepared by the method for preparing the electrolyte of example 1, except that fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, phthalic anhydride, pyromellitic anhydride, triphenyl phosphite, dicyclohexylcarbodiimide, and glyceryl triacetate were added in the amounts of 7.00%, 1.00%, 0.05%, and 0.30% by mass of the total electrolyte, in this order, and lithium hexafluorophosphate in an amount of 10.00% by mass of the total electrolyte was finally added to the mixed solution. The rest components are non-aqueous organic solvents, and the mixture ratio is the same as that of the example 1. Wherein, glyceryl triacetate is used as the impregnating compound.
A lithium secondary battery DS11 was prepared according to the method of example 1 using the above electrolyte.
Comparative example 12
An electrolyte DA11 was prepared by the method for preparing the electrolyte of example 1, except that fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, phthalic anhydride, pyromellitic anhydride, triphenyl phosphite, dicyclohexylcarbodiimide, and glyceryl tripropionate were added in the amounts of 7.00%, 1.00%, 0.05%, and 0.30% by mass in this order, and lithium hexafluorophosphate in an amount of 10.00% by mass in total of the electrolyte was finally added to the mixed solution. The rest components are non-aqueous organic solvents, and the mixture ratio is the same as that of the example 1. Wherein, the glyceryl tripropionate is used as the impregnating compound.
A lithium secondary battery DS12 was prepared according to the method of example 1 using the above electrolyte.
Test experiments
The following experiments were carried out for the batteries obtained in all examples 1 to 9 and all comparative examples 1 to 12:
normal temperature cycle experiment: the battery with the negative electrode made of lithium titanate material in the comparative example and the embodiment is subjected to a charge-discharge cycle test at room temperature within the range of 1.5-3.5V at the charge-discharge rate of 0.5C/0.5C, the battery with the negative electrode made of graphite and silicon carbon is subjected to a charge-discharge cycle test at room temperature within the range of 3-5V at the charge-discharge rate of 0.5C/0.5C, the cycle discharge capacity is recorded and is divided by the 1 st cycle to obtain the discharge capacity, and the recording results are shown in the figures 1-10.
High temperature storage experiment: the batteries using lithium titanate materials as the negative electrodes in the comparative example and the example are charged and discharged for 3 times at room temperature at a charge and discharge rate of 0.5C/0.5C of 1.5-3.5V, and then charged to 3.5V at 0.5C, and the 3 rd discharge capacity is recorded. And (3) storing the battery in a 60 ℃ oven for 7 days, cooling the battery to room temperature, charging and discharging for 3 times at 1.5-3.5V at the charge-discharge rate of 0.5C/0.5C at the room temperature, and recording the 1 st discharge capacity and the 3 rd discharge capacity. The 1 st discharge capacity after storage is divided by the 3 rd discharge capacity before storage to obtain a capacity retention rate, the 3 rd discharge capacity after storage is divided by the 3 rd discharge capacity before storage to obtain a capacity recovery rate, and the results are recorded in table 1.
The negative electrodes of the comparative example and the example are graphite and silicon carbon batteries, and the 3 rd discharge capacity is recorded after the batteries are charged and discharged for 3 times at room temperature at 3-5V with the charge and discharge rate of 0.5C/0.5C and then charged to 5V at 0.5C. And (3) storing the battery in a 60 ℃ oven for 7 days, cooling the battery to room temperature, charging and discharging for 3 times at 3-5V at room temperature by using a charging and discharging rate of 0.5C/0.5C, and recording the 1 st discharging capacity and the 3 rd discharging capacity. The 1 st discharge capacity after storage is divided by the 3 rd discharge capacity before storage to obtain a capacity retention rate, the 3 rd discharge capacity after storage is divided by the 3 rd discharge capacity before storage to obtain a capacity recovery rate, and the results are recorded in table 1.
Table 1: test results of capacity retention rate and capacity recovery rate of lithium secondary battery
The results, taken together with fig. 1, fig. 2 and table 1, show that: compared with SD1 and SD2 in S1 and S2, the negative electrode film-forming agent additive is added into the electrolyte, so that the cycle performance and the high-temperature storage performance of the battery are obviously improved, and the results show that fluoroethylene carbonate and vinylene carbonate can form a film on the surface of a negative electrode material, and the performance of the battery is improved.
The results, taken together with fig. 3, 4,5 and table 1, show that: compared with DS3, S4 and SD4, and S5 and SD5, the positive electrode film-forming additive phenyl anhydride compound is added into the electrolyte, so that the cycle performance and the high-temperature storage performance of the battery are obviously improved, and the phenyl anhydride can form a film on the surface of a positive electrode material, reduce the direct contact between the electrolyte and the positive electrode, reduce the oxidative decomposition reaction of the electrolyte and improve the performance of the battery.
The results, taken together with fig. 6, fig. 7 and table 1, show that: compared with SD6 and SD7 in S6 and S7, the stabilizing agents triphenyl phosphite and dicyclohexyl carbodiimide are added into the electrolyte, so that the cycle performance and high-temperature storage are obviously improved, the triphenyl phosphite and dicyclohexyl carbodiimide are shown to inhibit the side reaction decomposition of the electrolyte and improve the battery performance.
The results, taken together with fig. 8, fig. 9 and table 1, show that: compared with SD8 and SD9 in S8 and S9, the impregnating compound tristearin and glycerol trioleate are added into the electrolyte, so that the cycle performance is obviously improved, and the results show that the tristearin and the glycerol trioleate improve the wettability of the electrolyte on a pole piece and improve the performance of the battery.
The results, taken together with fig. 10 and table 1, show that: s1 is compared with DS10, and triphenyl phosphite and dicyclohexylcarbodiimide are better as electrolyte stabilizers; s1 is compared with DS11 and DS12, and the effect of the tristearin and the triolein as the sizing agents is better;
according to the analysis, the electrolyte disclosed by the invention contains the combination of the phenyl anhydride and the impregnating compound, and the phenyl anhydride additive can form a protective film on the surface of the positive electrode material to protect the positive electrode material from being damaged in the high-temperature storage and circulation processes; the impregnating compound can enable the electrolyte to fully wet the pole piece, so that the cycle performance is improved. In addition, the electrolyte also contains a negative electrode film forming additive and a stabilizer. The four additive components are mutually cooperated and are an organic whole, and the cycle performance and the high-temperature performance of the 5V high-voltage lithium secondary battery can be effectively improved.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (4)
1. The electrolyte for the 5V high-voltage lithium secondary battery comprises a negative electrode film-forming additive, an electrolyte stabilizer, electrolyte lithium salt and a non-aqueous organic solvent, and is characterized by also comprising a positive electrode film-forming additive and a wetting agent; the electrolyte stabilizer is composed of one of triphenyl phosphite and dicyclohexylcarbodiimide, and accounts for 0.01-0.1% of the total mass of the electrolyte; the positive film-forming additive consists of phenyl anhydride substances, and accounts for 1-3% of the total mass of the electrolyte; the impregnating compound consists of one or two of glyceryl tristearate and glycerol trioleate, and accounts for 0.1-0.5% of the total mass of the electrolyte; the negative electrode film forming additive is composed of one or more of fluoroethylene carbonate, vinylene carbonate and ethylene carbonate, and accounts for 1-15% of the total mass of the electrolyte, and the phenyl anhydride substances are selected from one or more of the following structural formulas:
wherein R is1、R2、R3、R4And R5Independently selected from hydrogen or methyl.
2. The electrolyte for a 5V high-voltage lithium secondary battery according to claim 1, wherein the electrolyte lithium salt is any one of lithium hexafluorophosphate, lithium perchlorate, lithium bis-fluorosulfonylimide, and lithium hexafluoroarsenate, and accounts for 10 to 17% of the total mass of the electrolyte.
3. The electrolyte for a 5V high voltage lithium secondary battery according to claim 1, wherein the non-aqueous organic solvent consists of a plurality of Ethyl Methanesulfonate (EMS), sulfolane (TMS), n-Butylsulfone (BS), Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Ethyl Acetate (EA), Propyl Acetate (PA), Ethyl Propionate (EP), which accounts for 65-80% of the total mass of the electrolyte.
4. A5V high-voltage lithium secondary battery, which comprises a positive electrode material selected from one of lithium nickel manganese oxide, lithium cobalt phosphate and lithium manganese phosphate, and a negative electrode material selected from one of lithium titanate, graphite and silicon carbon, and is characterized in that the electrolyte of the lithium secondary battery is the electrolyte as claimed in any one of claims 1 to 3.
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| CN108598550A (en) * | 2018-04-19 | 2018-09-28 | 北京理工大学 | A kind of high security solid state composite electrolyte, preparation method and lithium battery |
| CN109216768B (en) * | 2018-10-08 | 2020-06-26 | 河南师范大学 | Lithium ion battery additive, lithium ion battery non-aqueous electrolyte containing additive and application |
| CN109888387B (en) * | 2019-02-01 | 2021-10-08 | 无锡凯帕德瑞科技有限公司 | Capacitor battery electrolyte and preparation method thereof |
| CN113839088A (en) * | 2020-06-23 | 2021-12-24 | 比亚迪股份有限公司 | Electrolyte for lithium ion battery and lithium ion battery |
| CN113659205A (en) * | 2021-08-12 | 2021-11-16 | 湖州昆仑亿恩科电池材料有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN116632353B (en) * | 2023-07-17 | 2023-10-13 | 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 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101847752A (en) * | 2010-05-26 | 2010-09-29 | 惠州市德赛聚能电池有限公司 | Additive of electrolytic solution of lithium ion battery |
| CN102082292A (en) * | 2010-12-24 | 2011-06-01 | 西安瑟福能源科技有限公司 | High-temperature lithium ion battery electrolyte and lithium ion battery |
| CN102324568A (en) * | 2011-09-15 | 2012-01-18 | 诺莱特科技(苏州)有限公司 | Electrolyte solution for improving swelling of lithium ion battery |
| CN102496740A (en) * | 2011-12-01 | 2012-06-13 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte for improving low temperature performance of lithium iron phosphate batteries and preparation method thereof |
| CN103346350A (en) * | 2013-06-27 | 2013-10-09 | 深圳市崧鼎科技有限公司 | Electrolyte for improving performance of lithium ion battery and battery |
| CN103618106A (en) * | 2013-10-14 | 2014-03-05 | 厦门大学 | Electrolyte for preventing lithium titanate battery flatulence, and lithium titanate battery |
| CN104466249A (en) * | 2014-12-30 | 2015-03-25 | 薛利 | Electrolyte of lithium ion battery taking lithium titanate as cathode |
| CN105428710A (en) * | 2015-12-21 | 2016-03-23 | 中盐安徽红四方锂电有限公司 | High-temperature electrolytic solution for large-capacity plastic-casing lithium ion battery |
| CN105895954A (en) * | 2016-05-05 | 2016-08-24 | 东莞市凯欣电池材料有限公司 | High-stability power battery electrolyte |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100428615B1 (en) * | 2000-01-21 | 2004-04-30 | 삼성에스디아이 주식회사 | A electrolyte for a lithium secondary battery |
| US6767671B2 (en) * | 2000-07-14 | 2004-07-27 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and secondary battery containing same |
| KR100462782B1 (en) * | 2002-06-18 | 2004-12-20 | 삼성에스디아이 주식회사 | Polymer electrolyte with good leakage-resistance and lithium battery employing the same |
| JP4348908B2 (en) * | 2002-07-25 | 2009-10-21 | 三菱化学株式会社 | Electrolyte and secondary battery |
-
2017
- 2017-10-26 CN CN201711012849.0A patent/CN107887647B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101847752A (en) * | 2010-05-26 | 2010-09-29 | 惠州市德赛聚能电池有限公司 | Additive of electrolytic solution of lithium ion battery |
| CN102082292A (en) * | 2010-12-24 | 2011-06-01 | 西安瑟福能源科技有限公司 | High-temperature lithium ion battery electrolyte and lithium ion battery |
| CN102324568A (en) * | 2011-09-15 | 2012-01-18 | 诺莱特科技(苏州)有限公司 | Electrolyte solution for improving swelling of lithium ion battery |
| CN102496740A (en) * | 2011-12-01 | 2012-06-13 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte for improving low temperature performance of lithium iron phosphate batteries and preparation method thereof |
| CN103346350A (en) * | 2013-06-27 | 2013-10-09 | 深圳市崧鼎科技有限公司 | Electrolyte for improving performance of lithium ion battery and battery |
| CN103618106A (en) * | 2013-10-14 | 2014-03-05 | 厦门大学 | Electrolyte for preventing lithium titanate battery flatulence, and lithium titanate battery |
| CN104466249A (en) * | 2014-12-30 | 2015-03-25 | 薛利 | Electrolyte of lithium ion battery taking lithium titanate as cathode |
| CN105428710A (en) * | 2015-12-21 | 2016-03-23 | 中盐安徽红四方锂电有限公司 | High-temperature electrolytic solution for large-capacity plastic-casing lithium ion battery |
| CN105895954A (en) * | 2016-05-05 | 2016-08-24 | 东莞市凯欣电池材料有限公司 | High-stability power battery electrolyte |
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