CN110233293A - A kind of electrolyte and its preparation process improving high-temperature lithium ion battery performance - Google Patents
A kind of electrolyte and its preparation process improving high-temperature lithium ion battery performance Download PDFInfo
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- CN110233293A CN110233293A CN201910664237.2A CN201910664237A CN110233293A CN 110233293 A CN110233293 A CN 110233293A CN 201910664237 A CN201910664237 A CN 201910664237A CN 110233293 A CN110233293 A CN 110233293A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/0569—Liquid materials characterised by the solvents
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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 lithium ion field of material technology, and in particular to improve the electrolyte and its preparation process of high-temperature lithium ion battery performance.The electrolyte provided by the invention for improving high-temperature lithium ion battery performance, including compounded organic solvent, compound additive, lithium salts electrolyte nano particle, the electrolyte internal resistance provided by the invention for improving high-temperature lithium ion battery performance is smaller, improve charge efficiency, it is unstable that battery under hot environment can be effectively relieved, cyclicity and the undesirable problem of invertibity capacity, moreover, the lithium ion battery prepared by using electrolyte provided by the invention, further improve lithium ion battery charge-discharge performance at low temperature, safety and the lower situation of energy density, it has a good application prospect.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of electrolysis for improving high-temperature lithium ion battery performance
Liquid and its preparation process.
Background technique
Energy density is big, output power is high, has extended cycle life the advantages that small with environmental pollution due to having for lithium ion battery
It is widely used in electric car and consumer electronics product, and the medium that electrolyte is transmitted as battery intermediate ion, in lithium
Play highly important role in ion battery.However, allowing it as power battery, lithium ion battery is required to need into one
Step improves.Currently, in lithium ion battery most commonly used positive electrode mainly have cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate and
LiFePO4 etc..Lithium-ion-power cell not only safety with research discovery using spinel lithium manganate as positive electrode
It is good, and there is heavy-current discharge characteristic well, the cycle life of battery is also long, and therefore, LiMn2O4 is living as anode
Property substance lithium ion battery be most competitive one of power battery at present.However, the high temperature cyclic performance of LiMn2O4 and
Its reversible capacity is unsatisfactory, limits it in various applications.It realizes large-scale industrialization, is such as used as electric car
Power battery, it is necessary to the disadvantage for overcoming stability under its hot environment, capacity attenuation fast.
The patent of invention of Chinese patent application CN201610170292.2A, which discloses open one kind, can take into account battery high-temperature
The non-aqueous electrolyte for lithium ion cell of cycle performance and low-temperature circulating performance, and the lithium ion battery using the electrolyte.Institute
Electrolyte is stated, lithium salts shown in nonaqueous solvents, additive and following general formula is included:
In formula, R1 and R2 are one of halogen.The invention is by changing the lithium salts in lithium-ion battery electrolytes
With a certain amount of film for additive of addition, so that impedance of the battery in cyclic process reduces, but the high/low temperature of battery is recycled
Performance and stability are not greatly improved, and battery durability is bad.
Therefore it provides a kind of electrolysis that can be effectively improved battery high/low temperature cycle performance, stability and reversible capacity
Liquid is this field urgent problem to be solved.
Summary of the invention
Aiming at the shortcomings in the prior art, the purpose of the present invention is to provide a kind of improvement high-temperature lithium ion battery performances
Electrolyte and its preparation process.The electrolyte internal resistance provided by the invention for improving high-temperature lithium ion battery performance is smaller, and raising is filled
Electrical efficiency, and unstable battery under hot environment, cyclicity and the undesirable problem of invertibity capacity can also be effectively relieved, no
Only in this way, further improving lithium ion battery at low temperature by using lithium ion battery prepared by electrolyte provided by the invention
Charge-discharge performance, safety and the lower situation of energy density, have a good application prospect.
Technical scheme is as follows:
A kind of electrolyte improving high-temperature lithium ion battery performance, including compounded organic solvent, compound additive, lithium salts electricity
Solve matter nanoparticle.
Further, the compounded organic solvent includes carbonate solvent, and the carbonate solvent is ethylene carbonate, carbon
Acid propylene ester, dimethyl carbonate, any two kinds in methyl propyl carbonate, the carbonate solvent in the compounded organic solvent account for electricity
Solve the 20%~55% of liquid gross mass.
Further, the compounded organic solvent further includes carboxylate solvent, the carboxylate solvent be gamma-butyrolacton,
Methyl acetate, propyl acetate, ethyl propionate, methyl butyrate, any one in ethyl butyrate, the carboxylate solvent accounts for electrolyte
The 15%~29% of gross mass.
Further, the compound additive include 4,4- diaminodiphenyl sulfide, 4,4- methyl-imino diphenyl sulfide,
Vinylene carbonate, N, N- dimethyl trifluoroacetamide, succinonitrile, two kinds and two or more groups in 1,3- propane sultone
Point, the compound additive accounts for the 12%~21% of electrolyte gross mass.
Further, the lithium salts electrolyte nano particle includes lithium hexafluoro phosphate nanoparticle, four lithium fluophosphate nanometers
Particle, pentafluorophenyl group imide li nanoparticle, trifluoromethyl sulfonic acid lithium nanoparticle, in dioxalic acid lithium borate nanoparticle
Two kinds and two or more components, the lithium salts electrolyte nano particle account for the 18%~30% of electrolyte gross mass.
Further, the lithium salts electrolyte nano particle is prepared by chemical vapour deposition technique.
It is another object of the invention to provide a kind of preparation sides of electrolyte for improving high-temperature lithium ion battery performance
Method includes the following steps:
S1, under inert gas protection, carries out distillation drying for each solvent in compounded organic solvent respectively, removes
Water obtains dry organic solvent；
S2, under -40 DEG C of frost point, nitrogen protection, drying organic solvent prepared by step S1 is uniformly mixed, is then added
Compound additive obtains mixed liquor A；
S3, lithium salts electrolyte nano particle obtained is slowly added in the mixed liquor A of step S2 preparation, is uniformly mixed,
To obtain the final product.
Compared with prior art, technical advantage of the invention is as follows:
(1) electrolyte provided by the invention for improving high-temperature lithium ion battery performance, using compounded organic solvent, compound adds
Add agent, lithium salts electrolyte nano particle composition, not only improves heat dispersal situations, but also effectively reduce the interior of electrolyte
Resistance improves charge efficiency, has a good application prospect.
(2) electrolyte provided by the invention for improving high-temperature lithium ion battery performance, compounded organic solvent are molten by carbonic ester
Agent and carboxylate solvent's composition, using any two in ethylene carbonate, propene carbonate, dimethyl carbonate, methyl propyl carbonate
Kind of carbonate solvent, it is addition gamma-butyrolacton, methyl acetate, propyl acetate, ethyl propionate, methyl butyrate, any in ethyl butyrate
It is undesirable that unstable battery under hot environment, cyclicity and invertibity capacity has not only been effectively relieved in a kind of carboxylate solvent
Problem also reduces the internal resistance of electrolyte, improves charge efficiency.
(3) electrolyte provided by the invention for improving high-temperature lithium ion battery performance, compound additive use 4,4- diamino
Base diphenyl sulfide, 4,4- methyl-imino diphenyl sulfide, vinylene carbonate, N, N- dimethyl trifluoroacetamide, succinonitrile, 1,
Two kinds in 3-N-morpholinopropanesulfonic acid lactone and two or more components are prepared, and improve the undesirable problem of invertibity capacity, not only
In this way, further improving the lower situation of energy density under lithium ion battery low temperature.
(4) electrolyte provided by the invention for improving high-temperature lithium ion battery performance, lithium salts electrolyte nano particle use
Lithium hexafluoro phosphate nanoparticle, four lithium fluophosphate nanoparticles, pentafluorophenyl group imide li nanoparticle, trifluoromethyl sulfonic acid lithium
Two kinds in nanoparticle, dioxalic acid lithium borate nanoparticle and two or more components are composed, and are reduced the internal resistance of cell, are mentioned
High recharge efficiency, moreover, further improving lithium ion battery, charge-discharge performance, safety and energy density are lower at low temperature
Situation, have excellent performance, have a good application prospect.
Specific embodiment
The specific embodiment of form by the following examples makees further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following embodiment.
Embodiment 1, a kind of electrolyte for improving high-temperature lithium ion battery performance
The electrolyte for improving high-temperature lithium ion battery performance, including compounded organic solvent, compound additive, lithium salts electricity
Solve matter nanoparticle.
The compounded organic solvent includes carbonate solvent, and the carbonate solvent is by ethylene carbonate, propene carbonate
2:7 in mass ratio is formed, and the carbonate solvent in the compounded organic solvent accounts for the 55% of electrolyte gross mass.
The compounded organic solvent further includes carboxylate solvent, and the carboxylate solvent is gamma-butyrolacton, the carboxylate
Solvent accounts for the 15% of electrolyte gross mass.
The compound additive is by 4,4- diaminodiphenyl sulfide, 4,4- methyl-imino diphenyl sulfide 1:10 in mass ratio
Composition, the compound additive account for the 12% of electrolyte gross mass.
The lithium salts electrolyte nano particle by lithium hexafluoro phosphate nanoparticle, four lithium fluophosphate nanoparticles in mass ratio
12:7 composition, the lithium salts electrolyte nano particle account for the 18% of electrolyte gross mass.
The lithium salts electrolyte nano particle is prepared by chemical vapour deposition technique.
The preparation method of the electrolyte for improving high-temperature lithium ion battery performance, includes the following steps:
S1, under inert gas protection, carries out distillation drying for each solvent in compounded organic solvent respectively, removes
Water obtains dry organic solvent；
S2, under -40 DEG C of frost point, nitrogen protection, drying organic solvent prepared by step S1 is uniformly mixed, is then added
Compound additive obtains mixed liquor A；
S3, lithium salts electrolyte nano particle obtained is slowly added in the mixed liquor A of step S2 preparation, is uniformly mixed,
To obtain the final product.
Embodiment 2, a kind of electrolyte for improving high-temperature lithium ion battery performance
The electrolyte for improving high-temperature lithium ion battery performance, including compounded organic solvent, compound additive, lithium salts electricity
Solve matter nanoparticle.
The compounded organic solvent includes carbonate solvent, and the carbonate solvent is by ethylene carbonate, dimethyl carbonate
2:13 in mass ratio is formed, and the carbonate solvent in the compounded organic solvent accounts for the 30% of electrolyte gross mass.
The compounded organic solvent further includes carboxylate solvent, and the carboxylate solvent is methyl acetate, the carboxylate
Solvent accounts for the 29% of electrolyte gross mass.
The compound additive is 4,4- methyl-imino diphenyl sulfide, vinylene carbonate, 15:8 in mass ratio are formed,
The compound additive accounts for the 15% of electrolyte gross mass.
Further, the lithium salts electrolyte nano particle includes lithium hexafluoro phosphate nanoparticle, four lithium fluophosphate nanometers
Particle, pentafluorophenyl group imide li nanoparticle, trifluoromethyl sulfonic acid lithium nanoparticle, in dioxalic acid lithium borate nanoparticle
Two kinds and two or more components, the lithium salts electrolyte nano particle account for the 26% of electrolyte gross mass.
The lithium salts electrolyte nano particle is prepared by chemical vapour deposition technique.
The preparation method of the electrolyte for improving high-temperature lithium ion battery performance, includes the following steps:
S1, under inert gas protection, carries out distillation drying for each solvent in compounded organic solvent respectively, removes
Water obtains dry organic solvent；
S2, under -40 DEG C of frost point, nitrogen protection, drying organic solvent prepared by step S1 is uniformly mixed, is then added
Compound additive obtains mixed liquor A；
S3, lithium salts electrolyte nano particle obtained is slowly added in the mixed liquor A of step S2 preparation, is uniformly mixed,
To obtain the final product.
Embodiment 3, a kind of electrolyte for improving high-temperature lithium ion battery performance
The electrolyte for improving high-temperature lithium ion battery performance, including compounded organic solvent, compound additive, lithium salts electricity
Solve matter nanoparticle.
The compounded organic solvent includes carbonate solvent, and the carbonate solvent is by dimethyl carbonate, methyl propyl carbonate
4:9 in mass ratio is formed, and the carbonate solvent in the compounded organic solvent accounts for the 36% of electrolyte gross mass.
The compounded organic solvent further includes carboxylate solvent, and the carboxylate solvent is methyl butyrate, the carboxylate
Solvent accounts for the 22% of electrolyte gross mass.
For the compound additive by N, N- dimethyl trifluoroacetamide, succinonitrile 6:11 in mass ratio composition are described compound
Additive accounts for the 17% of electrolyte gross mass.
The lithium salts electrolyte nano particle is micro- by pentafluorophenyl group imide li nanoparticle, trifluoromethyl sulfonic acid lithium nanometer
Grain, dioxalic acid lithium borate nanoparticle 1:7:3 in mass ratio composition, the lithium salts electrolyte nano particle account for electrolyte gross mass
25%.
The lithium salts electrolyte nano particle is prepared by chemical vapour deposition technique.
The preparation method of the electrolyte for improving high-temperature lithium ion battery performance, includes the following steps:
S1, under inert gas protection, carries out distillation drying for each solvent in compounded organic solvent respectively, removes
Water obtains dry organic solvent；
S2, under -40 DEG C of frost point, nitrogen protection, drying organic solvent prepared by step S1 is uniformly mixed, is then added
Compound additive obtains mixed liquor A；
S3, lithium salts electrolyte nano particle obtained is slowly added in the mixed liquor A of step S2 preparation, is uniformly mixed,
To obtain the final product.
Embodiment 4, a kind of electrolyte for improving high-temperature lithium ion battery performance
The electrolyte for improving high-temperature lithium ion battery performance, including compounded organic solvent, compound additive, lithium salts electricity
Solve matter nanoparticle.
The compounded organic solvent includes carbonate solvent, and the carbonate solvent is by dimethyl carbonate, methyl propyl carbonate
4:9 in mass ratio is formed, and the carbonate solvent in the compounded organic solvent accounts for the 42% of electrolyte gross mass.
The compounded organic solvent further includes carboxylate solvent, and the carboxylate solvent is ethyl propionate, the carboxylate
Solvent accounts for the 27% of electrolyte gross mass.
The compound additive is by 4,4- diaminodiphenyl sulfide, N, N- dimethyl trifluoroacetamide, succinonitrile, 1,3- third
Sultones 5:3:12:1 in mass ratio composition, the compound additive account for the 19% of electrolyte gross mass.
The lithium salts electrolyte nano particle by lithium hexafluoro phosphate nanoparticle, pentafluorophenyl group imide li nanoparticle,
Dioxalic acid lithium borate nanoparticle 10:8:3 in mass ratio composition, the lithium salts electrolyte nano particle account for electrolyte gross mass
20%.
The lithium salts electrolyte nano particle is prepared by chemical vapour deposition technique.
The preparation method of the electrolyte for improving high-temperature lithium ion battery performance, includes the following steps:
S1, under inert gas protection, carries out distillation drying for each solvent in compounded organic solvent respectively, removes
Water obtains dry organic solvent；
S2, under -40 DEG C of frost point, nitrogen protection, drying organic solvent prepared by step S1 is uniformly mixed, is then added
Compound additive obtains mixed liquor A；
S3, lithium salts electrolyte nano particle obtained is slowly added in the mixed liquor A of step S2 preparation, is uniformly mixed,
To obtain the final product.
Embodiment 5, a kind of lithium ion battery
Lithium ion battery is prepared using the method for Chinese patent CN201610170292.2A embodiment 1, wherein by electrolyte
Replace with the electrolyte of the improvement high-temperature lithium ion battery performance of the preparation of embodiment 1.
Embodiment 6, a kind of lithium ion battery
Lithium ion battery is prepared using the method for Chinese patent CN201610170292.2A embodiment 1, wherein by electrolyte
Replace with the electrolyte of the improvement high-temperature lithium ion battery performance of the preparation of embodiment 2.
Embodiment 7, a kind of lithium ion battery
Lithium ion battery is prepared using the method for Chinese patent CN201610170292.2A embodiment 1, wherein by electrolyte
Replace with the electrolyte of the improvement high-temperature lithium ion battery performance of the preparation of embodiment 3.
Embodiment 8, a kind of lithium ion battery
Lithium ion battery is prepared using the method for Chinese patent CN201610170292.2A embodiment 1, wherein by electrolyte
Replace with the electrolyte of the improvement high-temperature lithium ion battery performance of the preparation of embodiment 4.
Comparative example 1, a kind of electrolyte for improving high-temperature lithium ion battery performance
The electrolyte for improving high-temperature lithium ion battery performance, including compounded organic solvent, compound additive, lithium salts electricity
Solve matter nanoparticle.
The compounded organic solvent is carbonate solvent, and the carbonate solvent is pressed by dimethyl carbonate, methyl propyl carbonate
Mass ratio 4:9 is formed, and the carbonate solvent in the compounded organic solvent accounts for the 58% of electrolyte gross mass.
For the compound additive by N, N- dimethyl trifluoroacetamide, succinonitrile 6:11 in mass ratio composition are described compound
Additive accounts for the 17% of electrolyte gross mass.
The lithium salts electrolyte nano particle is micro- by pentafluorophenyl group imide li nanoparticle, trifluoromethyl sulfonic acid lithium nanometer
Grain, dioxalic acid lithium borate nanoparticle 1:7:3 in mass ratio composition, the lithium salts electrolyte nano particle account for electrolyte gross mass
25%.
The preparation method of the lithium salts electrolyte nano particle and the electrolyte of improvement high-temperature lithium ion battery performance, with reality
It is identical to apply example 3.
Comparative example 1 is substantially the same manner as Example 3, and difference is, carboxylate solvent replaces in compounded organic solvent in comparative example 1
It is changed to the carbonate solvent of identical mass percent.
Comparative example 2, a kind of electrolyte for improving high-temperature lithium ion battery performance
The electrolyte for improving high-temperature lithium ion battery performance, including compounded organic solvent, additive, lithium salts electrolyte
Nanoparticle.
The compounded organic solvent includes carbonate solvent, and the carbonate solvent is by dimethyl carbonate, methyl propyl carbonate
4:9 in mass ratio is formed, and the carbonate solvent in the compounded organic solvent accounts for the 36% of electrolyte gross mass.
The compounded organic solvent further includes carboxylate solvent, and the carboxylate solvent is methyl butyrate, the carboxylate
Solvent accounts for the 22% of electrolyte gross mass.
The additive is N, and N- dimethyl trifluoroacetamide, the additive accounts for the 17% of electrolyte gross mass.
The lithium salts electrolyte nano particle is micro- by pentafluorophenyl group imide li nanoparticle, trifluoromethyl sulfonic acid lithium nanometer
Grain, dioxalic acid lithium borate nanoparticle 1:7:3 in mass ratio composition, the lithium salts electrolyte nano particle account for electrolyte gross mass
25%.
The preparation method of the lithium salts electrolyte nano particle and the electrolyte of improvement high-temperature lithium ion battery performance, with reality
It is identical to apply example 3.
Comparative example 2 is substantially the same manner as Example 3, and difference is, additive uses one-component N, N- diformazan in comparative example 2
Base trifluoroacetamide.
Comparative example 3, a kind of electrolyte for improving high-temperature lithium ion battery performance
The electrolyte for improving high-temperature lithium ion battery performance, including compounded organic solvent, compound additive, lithium salts electricity
Xie Zhi.
The compounded organic solvent includes carbonate solvent, and the carbonate solvent is by dimethyl carbonate, methyl propyl carbonate
4:9 in mass ratio is formed, and the carbonate solvent in the compounded organic solvent accounts for the 36% of electrolyte gross mass.
The compounded organic solvent further includes carboxylate solvent, and the carboxylate solvent is methyl butyrate, the carboxylate
Solvent accounts for the 22% of electrolyte gross mass.
For the compound additive by N, N- dimethyl trifluoroacetamide, succinonitrile 6:11 in mass ratio composition are described compound
Additive accounts for the 17% of electrolyte gross mass.
The lithium salts electrolyte by pentafluorophenyl group imide li, trifluoromethyl sulfonic acid lithium, dioxalic acid lithium borate in mass ratio
1:7:3 composition, the lithium salts electrolyte account for the 25% of electrolyte gross mass.
The preparation method of the electrolyte for improving high-temperature lithium ion battery performance, it is same as Example 3.
Comparative example 3 is substantially the same manner as Example 3, and difference is, lithium salts electrolyte does not use nanoparticle in comparative example 3.
Comparative example 4, a kind of electrolyte for improving high-temperature lithium ion battery performance
The electrolyte for improving high-temperature lithium ion battery performance, including organic solvent, compound additive, lithium salts electrolyte
Nanoparticle.
The organic solvent is carboxylate solvent, and the carboxylate solvent is methyl butyrate, and the carboxylate solvent accounts for electricity
Solve the 58% of liquid gross mass.
For the compound additive by N, N- dimethyl trifluoroacetamide, succinonitrile 6:11 in mass ratio composition are described compound
Additive accounts for the 17% of electrolyte gross mass.
The lithium salts electrolyte nano particle is micro- by pentafluorophenyl group imide li nanoparticle, trifluoromethyl sulfonic acid lithium nanometer
Grain, dioxalic acid lithium borate nanoparticle 1:7:3 in mass ratio composition, the lithium salts electrolyte nano particle account for electrolyte gross mass
25%.
The preparation method of the lithium salts electrolyte nano particle and the electrolyte of improvement high-temperature lithium ion battery performance, with reality
It is identical to apply example 3.
Comparative example 4 is substantially the same manner as Example 3, and difference is, carbonate solvent replaces in organic solvent in comparative example 4
The carboxylate solvent of identical mass percent.
Comparative example 5, a kind of lithium ion battery
Lithium ion battery is prepared using the method for Chinese patent CN201610170292.2A embodiment 1, wherein by electrolyte
Replace with the electrolyte of the improvement high-temperature lithium ion battery performance of the preparation of comparative example 1.
Comparative example 6, a kind of lithium ion battery
Lithium ion battery is prepared using the method for Chinese patent CN201610170292.2A embodiment 1, wherein by electrolyte
Replace with the electrolyte of the improvement high-temperature lithium ion battery performance of the preparation of comparative example 2.
Comparative example 7, a kind of lithium ion battery
Lithium ion battery is prepared using the method for Chinese patent CN201610170292.2A embodiment 1, wherein by electrolyte
Replace with the electrolyte of the improvement high-temperature lithium ion battery performance of the preparation of comparative example 3.
Comparative example 8, a kind of lithium ion battery
Lithium ion battery is prepared using the method for Chinese patent CN201610170292.2A embodiment 1, wherein by electrolyte
Replace with the electrolyte of the improvement high-temperature lithium ion battery performance of the preparation of comparative example 4.
45 DEG C of test example one, battery cycle performance tests
1. the lithium ion battery of test material embodiment 5-8 and comparative example 5-8 preparation.
2. test method: at 45 DEG C, by test material with 1C constant-current charge to 4.40V, then constant-voltage charge to electric current is
0.05C, then with 1C constant-current discharge to 3.0V, such charge/discharge, calculate separately circulating battery 50 times, 100 times, 300 times and
Capacity retention ratio after 500 times.
3. test result: 45 DEG C of cycle performance test results of battery are shown in Table 1.
Capacity retention ratio (%)=n-th circulation discharge capacity/discharge capacity for the first time after lithium ion battery n times circulation
× 100%.
Table 1 battery, 45 DEG C of cycle performance test datas
As shown in Table 1, the capacity retention ratio after lithium ion battery 500 times circulations of embodiment 5-8 preparation is all larger than
77.4%, 1.0C and 2.0C multiplying power discharge capacity than being respectively greater than 89.8% and 87.0%, lithium that wherein prepared by embodiment 7 from
Sub- battery performance is best, is highly preferred embodiment of the present invention, in contrast, lithium ion battery 500 times of comparative example 5-8 preparation are followed
Capacity retention ratio after ring is respectively less than 67.6%, 1.0C and 2.0C multiplying power discharge capacity ratio is respectively smaller than 84.6% He
80.9%, performance is poor, and test result shows the electrolyte preparation provided by the invention for improving high-temperature lithium ion battery performance
The invertibity capacity of battery is improved, and has good cyclical stability.
60 DEG C of test example two, lithium ion battery storage tests
1. the lithium ion battery of test material embodiment 5-8 and comparative example 5-8 preparation.
2. test method: respectively by test material at room temperature with 0.5C constant-current charge to 4.40V, then constant-voltage charge to electricity
Stream is 0.05C, tests the thickness of lithium ion battery and is denoted as h0；Then above-mentioned test material is put into 60 DEG C of constant temperature respectively
Case keeps the temperature 30 days, and every the thickness of 5 days test lithium ion batteries and is denoted as hn, n is the day of high-temperature lithium ion battery storage
Number.
3. test result: 60 DEG C of storage test results of lithium ion battery are shown in Table 2.
Thickness swelling (%)=(h after high-temperature lithium ion battery storage n daysn-h0)/h0× 100%.
2 lithium ion battery of table, 60 DEG C of storage test datas
As shown in Table 2, the thickness swelling behind 60 DEG C of lithium ion battery storages 30 days of embodiment 5-8 preparation is respectively less than
7.2%, the performance of lithium ion battery that wherein prepared by embodiment 7 is best, is highly preferred embodiment of the present invention, in contrast, comparison
Thickness swelling behind 60 DEG C of lithium ion battery storages 30 days of example 5-8 preparation is all larger than 11.3%, and performance is poor, test result
Show that the storge quality of the battery of the electrolyte preparation provided by the invention for improving high-temperature lithium ion battery performance at high temperature obtains
To raising, have a good application prospect.
The low temperature performance test of test example three, lithium ion battery
1. the lithium ion battery of test material embodiment 5-8 and comparative example 5-8 preparation.
2. test method: at 25 DEG C, above-mentioned test material lithium ion battery being stood 30min respectively, later with 0.5C
Constant-current charge is to 4.4V, and constant-voltage charge exists lithium ion battery to 0.05C, and after standing 5min respectively at 4.4V later
Static 4h under different temperatures (25 DEG C, 0 DEG C, -10 DEG C), is then discharged to 3.0V with 0.5C, and electric discharge terminates and then stands every time
5min records the discharge capacity of lithium ion battery.On the basis of 25 DEG C of discharge capacities, lithium ion battery is obtained at different temperatures
Discharge capacity ratio.
3. test result: lithium ion battery low temperature performance test result is shown in Table 3.
Electric discharge under discharge capacity ratio (%)=different temperatures (0 DEG C, -10 DEG C) under lithium ion battery different temperatures is held
Measure/25 DEG C of discharge capacity × 100%.
The low temperature performance test data of 3 lithium ion battery of table
As shown in Table 3, discharge capacity ratio of the lithium ion battery of embodiment 5-8 preparation at 0 DEG C and -10 DEG C is all larger than
89.8%, the performance of lithium ion battery that wherein prepared by embodiment 7 is best, is highly preferred embodiment of the present invention, in contrast, comparison
Discharge capacity of the lithium ion battery of example 5-8 preparation at 0 DEG C and -10 DEG C is than being respectively less than 88.2%, and performance is poor, test result
Show that the discharge capacity of the battery of the electrolyte preparation provided by the invention for improving high-temperature lithium ion battery performance at low temperature obtains
To raising, have a good application prospect.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (7)
1. a kind of electrolyte for improving high-temperature lithium ion battery performance, which is characterized in that including compounded organic solvent, compound addition
Agent, lithium salts electrolyte nano particle.
2. improving the electrolyte of high-temperature lithium ion battery performance as described in claim 1, which is characterized in that described compound organic
Solvent includes carbonate solvent, and the carbonate solvent is ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid first third
Any two kinds in ester, the carbonate solvent in the compounded organic solvent accounts for the 20%~55% of electrolyte gross mass.
3. improving the electrolyte of high-temperature lithium ion battery performance as described in claim 1, which is characterized in that described compound organic
Solvent further includes carboxylate solvent, and the carboxylate solvent is gamma-butyrolacton, methyl acetate, propyl acetate, ethyl propionate, fourth
Any one in sour methyl esters, ethyl butyrate, the carboxylate solvent account for the 15%~29% of electrolyte gross mass.
4. improving the electrolyte of high-temperature lithium ion battery performance as described in claim 1, which is characterized in that the compound addition
Agent includes 4,4- diaminodiphenyl sulfide, 4,4- methyl-imino diphenyl sulfide, vinylene carbonate, N, N- dimethyl trifluoro second
Amide, succinonitrile, two kinds and two or more components in 1,3-propane sultone, the compound additive account for electrolyte gross mass
12%~21%.
5. improving the electrolyte of high-temperature lithium ion battery performance as described in claim 1, which is characterized in that the lithium salts electrolysis
Matter nanoparticle include lithium hexafluoro phosphate nanoparticle, four lithium fluophosphate nanoparticles, pentafluorophenyl group imide li nanoparticle,
Two kinds in trifluoromethyl sulfonic acid lithium nanoparticle, dioxalic acid lithium borate nanoparticle and two or more components, the lithium salts electricity
Solution matter nanoparticle accounts for the 18%~30% of electrolyte gross mass.
6. improving the electrolyte of high-temperature lithium ion battery performance as described in claim 1, which is characterized in that the lithium salts electrolysis
Matter nanoparticle is prepared by chemical vapour deposition technique.
7. a kind of preparation method of the electrolyte as claimed in any one of claims 1 to 6 for improving high-temperature lithium ion battery performance,
It is characterized by comprising the following steps:
S1, under inert gas protection, carries out distillation drying for each solvent in compounded organic solvent respectively, removes water, obtains
To dry organic solvent；
S2, under -40 DEG C of frost point, nitrogen protection, drying organic solvent prepared by step S1 is uniformly mixed, is then added compound
Additive obtains mixed liquor A；
S3, lithium salts electrolyte nano particle obtained is slowly added to step S2 preparation mixed liquor A in, be uniformly mixed to get.
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