CN115425292A - High-temperature-resistant electrolyte, secondary battery and application thereof - Google Patents

High-temperature-resistant electrolyte, secondary battery and application thereof Download PDF

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CN115425292A
CN115425292A CN202210978186.2A CN202210978186A CN115425292A CN 115425292 A CN115425292 A CN 115425292A CN 202210978186 A CN202210978186 A CN 202210978186A CN 115425292 A CN115425292 A CN 115425292A
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electrolyte
temperature
polyfluorobenzene
lithium
compound
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谢佳
曾子琪
张涵
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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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
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • 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 provides a high-temperature-resistant electrolyte, a secondary battery and application thereof, wherein the high-temperature-resistant electrolyte comprises a polyfluorobenzene compound, a lithium salt and a solvent, and the electrolyte containing the polyfluorobenzene compound is adopted at high temperature, so that on one hand, the decomposition of the electrolyte can be relieved, hydrofluoric acid is generated, the dissolution of transition metal ions of a positive electrode is reduced, the high-temperature cycle performance and the high-temperature storage stability of the battery are improved, on the other hand, a certain film forming property is realized, a stable interface protective film is formed, and the cycle life of the battery is prolonged.

Description

High-temperature-resistant electrolyte, secondary battery and application thereof
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a high-temperature-resistant electrolyte, a secondary battery and application thereof.
Background
A secondary battery (Rechargeable battery) is also called a Rechargeable battery or a secondary battery, and refers to a battery that can be continuously used by activating an active material by charging after the battery is discharged. The secondary battery has the characteristics of high energy density, high power density, environmental friendliness and the like, and is widely applied to the fields of portable electronic products, power automobiles and the like.
Currently, fluoroethylene carbonate (FEC) is used as an additive in a commercial electrolyte for a secondary battery. In an electrolyte system containing FEC, lithium hexafluorophosphate is easy to react with trace water in the electrolyte at high temperature, lewis acid is generated by decomposition, acidic substances such as hydrofluoric acid and the like are generated by catalyzing the decomposition of FEC, the acidic substances can promote the further decomposition of lithium hexafluorophosphate, and meanwhile, the acidic substances can attack positive transition metal ions to dissolve out the transition metal ions, so that the cycle performance of the battery is rapidly reduced.
Disclosure of Invention
Based on this, it is necessary to provide a high temperature resistant electrolyte, a secondary battery and applications thereof, which can avoid the problems caused by the decomposition and acid production of FEC, and ensure the advantage of high temperature resistant cycle performance of the battery.
The invention adopts the following technical scheme:
the invention provides a high-temperature-resistant electrolyte, which comprises a solvent, lithium salt and an additive, wherein the additive does not contain fluoroethylene carbonate, the additive at least contains a polyfluorobenzene compound, and the mass percent of the polyfluorobenzene compound in the electrolyte is 0.1-10%.
In some of these embodiments, the polyfluorobenzene compound is selected from at least one of 1, 2-difluorobenzene, 1, 3-difluorobenzene, 1, 4-difluorobenzene, 1,2, 3-trifluorobenzene, 1,2, 4-trifluorobenzene, 1,3, 5-trifluorobenzene, trifluorotoluene, trifluoromethoxybenzene.
In some of these embodiments, the additive further comprises at least one of fluorinated carbonate, lithium nitrate, lithium fluoride, vinylene carbonate, diphenylethane, dimethylacetamide, isatoic anhydride, 4, 5-dicyano-2- (trifluoromethyl) imidazole, 5-acetylthiophene-2-carbonitrile, N-dimethylformamide, (2-allylphenoxy) trimethylsilane, benzoic anhydride, tris (trimethylsilane) phosphite, 1- (dimethylamino) pyrrole, 4, 5-dicyano-2- (trifluoromethyl) imidazole, p-toluenesulfonylmethylisonitrile. The adding amount of 5-acetylthiophene-2-carbonitrile, 1- (dimethylamino) pyrrole, (2-allylphenoxy) trimethylsilane, 4, 5-dicyano-2- (trifluoromethyl) imidazole and p-toluenesulfonylmethylisocyanamide accounts for 0.5-1% by mass of the electrolyte.
In some of these embodiments, the additive further comprises 5-acetylthiophene-2-carbonitrile, and the mass ratio of the polyfluorobenzene compound to the 5-acetylthiophene-2-carbonitrile is 20.
In some embodiments, the additive further comprises 1- (dimethylamino) pyrrole, and the mass ratio of the polyfluorobenzene compound to the 1- (dimethylamino) pyrrole is 10.
In some of these embodiments, the additive further comprises (2-allylphenoxy) trimethylsilane, and the mass ratio of polyfluorobenzene compound to (2-allylphenoxy) trimethylsilane is 10.
In some of these embodiments, the additive further comprises 4, 5-dicyano-2- (trifluoromethyl) imidazole, and the mass ratio of polyfluorobenzene compound to 4, 5-dicyano-2- (trifluoromethyl) imidazole is 10.
In some of these embodiments, the additive further comprises p-toluenesulfonylmethyl isonitrile, and the mass ratio of the polyfluorobenzene compound to the p-toluenesulfonylmethyl isonitrile is 10.
The invention provides application of the high-temperature resistant electrolyte in preparation of a secondary battery.
The invention provides a high-temperature resistant secondary battery, which comprises a positive electrode material, a negative electrode material, a diaphragm and the high-temperature resistant electrolyte. The anode material is selected from one or more of lithium iron phosphate, lithium cobaltate, lithium titanate, lithium manganate, ternary nickel cobalt manganese and ternary nickel cobalt aluminum. The negative electrode material is selected from at least one of graphite, a silicon negative electrode and a metal negative electrode.
In some embodiments, the solvent of the high-temperature electrolyte is selected from one or more of an ether organic solvent, an ester organic solvent and an ether-ester mixed organic solvent electrolyte.
In some of these embodiments, the separator is selected from the group consisting of a PP separator, a PE separator, a PP/PE/PP separator, al 2 O 3 Coating diaphragm, glass fiber diaphragm, PVDF diaphragm, PET/Al 2 O 3 One or more of a diaphragm, a cellulose diaphragm and an aramid diaphragm.
Compared with the prior art, the invention has the beneficial effects that:
the electrolyte of fluoroethylene carbonate is replaced by the polyfluorobenzene compound, so that the polyfluorobenzene compound has stable thermodynamic property, hydrofluoric acid is not easy to generate through a beta-H elimination mechanism, the decomposition of the electrolyte can be relieved at high temperature (30-70 ℃) to generate an acidic substance on the whole, the dissolution of transition metal ions of a positive electrode is reduced, the high-temperature (30-70 ℃) cycle performance and the high-temperature storage stability of the battery are improved, and the polyfluorobenzene compound has good electrochemical property, can be decomposed at a negative electrode before a solvent, has certain film forming property, forms a stable interface protective film rich in inorganic substances and lithium fluoride, and improves the cycle life of the battery. In addition, the electrolyte adopting the polyfluorobenzene compound to replace fluoroethylene carbonate has obvious cost advantage.
Drawings
Fig. 1 is a plot of the LSV negative scan of cells assembled using electrolytes prepared in example 1 and comparative example 1.
Fig. 2 is a graph showing cycle curves of Li-NCM622 batteries assembled using the electrolytes prepared in example 1 and comparative example 1, tested in a high temperature environment of 3 to 4.3V, 1C rate, 60 ℃.
Fig. 3 is a graph showing cycle profiles of the Li-NCM622 battery assembled using the electrolytes prepared in example 1 and comparative example 1, tested under a high temperature environment of 60℃ at 1C charge and 2C discharge.
Fig. 4 is a graph showing the cycle curve of the graphite battery assembled using the electrolytes prepared in example 1 and comparative example 1 under a high temperature condition of 60 c.
Fig. 5 is a graph showing the cycle profile of a silicon oxide cell assembled using the electrolytes prepared in example 1 and comparative example 1 under a high temperature condition of 60 ℃.
Detailed Description
The present invention is further described in detail below with reference to specific examples so that those skilled in the art can more clearly understand the present invention.
The following examples are provided only for illustrating the present invention, and are not intended to limit the scope of the present invention. All other embodiments obtained by a person skilled in the art based on the specific embodiments of the present invention without any inventive step are within the scope of the present invention.
In the examples of the present invention, all the raw material components are commercially available products well known to those skilled in the art, unless otherwise specified; in the examples of the present invention, unless otherwise specified, all technical means used are conventional means well known to those skilled in the art.
Reagent Density (g cm) –3 ) Price ($ for 100 g)
Fluoroethylene carbonate 1.454 795
Trifluoro benzene 1.26～1.28 35～90
Difluoro substituted benzene 1.11～1.16 7～40
Trifluoromethyl benzene 1.19 5～15
Trifluoromethoxybenzene 1.226 30
Example 1
The embodiment provides an electrolyte, and a preparation method thereof comprises the following steps: a mixed solvent of ethylene carbonate and diethyl carbonate was prepared in a volume ratio of 1.
Comparative example 1
This comparative example provides an electrolyte prepared essentially as in example 1, except that: equal amounts of FEC were used instead of equal amounts of 1,3, 5-trifluorobenzene.
The electrolytes of example 1 and comparative example 1 were tested separately: color and pH changes over five days of continuous storage at 50 ℃ ambient temperature, as shown in figure 1 and the following table:
Figure BDA0003799099330000051
assembly tests were carried out with different positive cells for the electrolytes of example 1 and comparative example 1, respectively:
(1) Battery assembly tests were performed using the electrolytes prepared in example 1 and comparative example 1, respectively: the stainless steel sheet, the diaphragm and the lithium sheet are assembled into a battery together in an argon-protected glove box, the electrolytes prepared in example 1 and comparative example 1 are respectively added, negative sweep characterization is carried out in a Chenghua electrochemical workstation, the negative sweep is carried out from 3V to 0V, and the obtained test curve is shown in figure 1. The results show that: the decomposition voltage of the battery assembled using the electrolyte prepared in example 1 was around 0.8V, which was higher than that of the battery assembled using the electrolyte prepared in comparative example 1.
(2) Lithium-ternary nickel cobalt manganese (Li-NCM 622) battery assembly tests were performed using the electrolytes prepared in example 1 and comparative example 1, respectively: the battery was assembled with a cathode material of ternary nickel cobalt manganese (NCM 622), separator, and lithium sheet in an argon-protected glove box, and the electrolytes prepared in example 1 and comparative example 1 were added, respectively.
The two groups of batteries were subjected to cycle testing in a high temperature environment of 60 ℃ with a 1C rate charge-discharge of 3-4.3V, respectively, and the results are shown in FIG. 2. The results show that: compared with the battery assembled by the electrolyte of the comparative example 1, the battery assembled by the electrolyte of the example 1 has the high-temperature cycle number of more than 200 circles, the capacity retention rate is still more than 50%, and the coulombic efficiency is more than 99%.
The two groups of batteries were placed at 3-4.3V, 1C charged and 2C discharged, respectively, and subjected to cycle testing at 60 ℃ in a high temperature environment, with the results shown in fig. 3. The results show that: compared with the battery assembled by the electrolyte of the comparative example 1, the battery assembled by the electrolyte of the example 1 has more than 400 cycles of high-temperature circulation, the capacity retention rate is still more than 70 percent, and the coulombic efficiency is more than 99 percent.
(3) The electrolytes prepared in example 1 and comparative example 1 were used for a graphite battery assembly test, respectively: graphite, a diaphragm and a lithium sheet were assembled together into a battery in an argon-protected glove box, and the electrolytes prepared in example 1 and comparative example 1 were added, respectively. The two groups of batteries are respectively placed under the conditions of 0.01-2V, 0.5C multiplying power charge-discharge and 60 ℃ high temperature for circulation, and the obtained circulation curve is shown in figure 4. The results show that: after the battery assembled by the electrolyte in the embodiment 1 is cycled for 100 circles at high temperature, the capacity retention rate exceeds 98%, the average coulombic efficiency is more than 99%, and the capacity retention rate is slightly higher than that of the battery assembled by the electrolyte in the comparative example 1 after the battery is cycled for 100 circles at 96%.
(4) The electrolytes prepared in example 1 and comparative example 1 were used for the assembly test of a silicon oxide cell: the battery was assembled with the silica, separator, and lithium sheet in an argon-protected glove box, and the electrolytes prepared in example 1 and comparative example 1 were added, respectively. The two groups of batteries are respectively placed under the conditions of 0.05-1.5V, 0.5C multiplying power charge-discharge and 60 ℃ high temperature for circulation, and the obtained circulation curve is shown in figure 5. The results show that: after the battery assembled by the electrolyte in the embodiment 1 is circulated for 40 circles at high temperature, the capacity retention rate is about 55%, the average coulombic efficiency is more than 97%, and the capacity retention rate is higher than that of the battery assembled by the electrolyte in the comparative example 1 after the battery is circulated for 40 circles by 43%.
Example 2
The embodiment provides an electrolyte, and a preparation method thereof includes the following steps: preparing a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 1.
Comparative example 2
This comparative example provides an electrolyte which differs from the electrode solution of example 2 only in that: equal amounts of FEC were used instead of equal amounts of 1,3, 5-trifluorobenzene.
Example 3
The embodiment provides an electrolyte, and a preparation method thereof includes the following steps: a mixed solvent of ethylene carbonate and diethyl carbonate was prepared in a volume ratio of 1.
Comparative example 3
This comparative example provides an electrolyte which differs from the electrode solution of example 3 only in that: equal amounts of FEC were used instead of equal amounts of 1,3, 5-trifluorobenzene.
Example 4
The embodiment provides an electrolyte, and a preparation method thereof comprises the following steps: preparing a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 1:1, adding lithium hexafluorophosphate to form a 1M lithium hexafluorophosphate solution, adding 1,3,5-trifluorobenzene thereto, and stirring to mix uniformly to form an electrolyte solution containing 2.5% by weight of 1,3,5-trifluorobenzene.
Comparative example 4
This comparative example provides an electrolyte which differs from the electrode solution of example 4 only in that: equal amounts of FEC were used instead of equal amounts of 1,3, 5-trifluorobenzene.
Example 5
The embodiment provides an electrolyte, and a preparation method thereof includes the following steps: preparing a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 1.
Comparative example 5
This comparative example provides an electrolyte which differs from the electrode solution of example 5 only in that: equal amounts of FEC were used instead of equal amounts of 1,3, 5-trifluorobenzene.
Example 6
The embodiment provides an electrolyte, and a preparation method thereof includes the following steps: taking a proper amount of ethylene glycol dimethyl ether solvent, adding lithium hexafluorophosphate to form a 1M lithium hexafluorophosphate solution, adding 1,2, 3-trifluorobenzene, and uniformly stirring to form an electrolyte containing 10wt% of 1,2, 3-trifluorobenzene.
Comparative example 6
This comparative example provides an electrolyte which differs from the electrolyte of example 6 only in that: equal amounts of FEC were used instead of equal amounts of 1,2, 3-trifluorobenzene.
Example 7
The embodiment provides an electrolyte, and a preparation method thereof comprises the following steps: preparing a volume ratio of 1:4, diethyl carbonate and 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, adding lithium hexafluorophosphate to form a 0.4M lithium hexafluorophosphate solution, adding 1,2, 4-trifluorobenzene thereto, and mixing them with stirring to form an electrolyte containing 1,2, 4-trifluorobenzene in an amount of 10wt%.
Comparative example 7
This comparative example provides an electrolyte that differs from the electrolyte of example 7 only in that: equal amounts of FEC were used instead of equal amounts of 1,2, 4-trifluorobenzene.
Example 8
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: additive 5wt%1,3,5-trifluorobenzene and 2wt% vinylene carbonate.
Comparative example 8
This comparative example provides an electrolyte which differs from example 8 only in that: equal amounts of FEC were used instead of equal amounts of 1,3, 5-trifluorobenzene.
Example 9
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: additive 5wt%, 1,3,5-trifluorobenzene and 1wt% lithium difluorophosphate.
Comparative example 9
The present comparative example provides an electrolyte which differs from example 9 only in that: equal amounts of FEC were used instead of equal amounts of 1,3, 5-trifluorobenzene.
Example 10
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: the lithium hexafluorophosphate is replaced by the same amount of lithium perchlorate.
Comparative example 10
This comparative example provides an electrolyte which differs from example 10 only in that: equal amounts of FEC were used instead of equal amounts of 1,3, 5-trifluorobenzene.
Example 11
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: 1,2-difluorobenzene as an additive in an amount of 1,0% by weight.
Comparative example 11
This comparative example provides an electrolyte which differs from example 11 only in that: equal amounts of FEC were used instead of equal amounts of 1, 2-difluorobenzene.
Example 12
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: 1,3-difluorobenzene as an additive by 10 wt%.
Comparative example 12
This comparative example provides an electrolyte which differs from example 12 only in that: equal amounts of FEC were used instead of equal amounts of 1, 3-difluorobenzene.
Example 13
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: 1,4-difluorobenzene as an additive by 10 wt%.
Comparative example 13
This comparative example provides an electrolyte which differs from example 13 only in that: equal amounts of FEC were used instead of equal amounts of 1, 4-difluorobenzene.
Example 14
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: the additive was 10wt% trifluorotoluene.
Comparative example 14
The present comparative example provides an electrolyte which differs from example 14 only in that: an equal amount of FEC was used instead of an equal amount of trifluorotoluene.
Example 15
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: the additive is 10wt% of trifluoromethoxybenzene.
Comparative example 15
This comparative example provides an electrolyte which differs from example 15 only in that: equal amounts of FEC were used instead of equal amounts of trifluoromethoxybenzene.
Lithium-ternary nickel cobalt manganese (Li-NCM 622) battery assembly tests were performed using the electrolytes prepared in examples 2 to 15 and comparative examples 2 to 15, respectively: the battery is assembled by the ternary nickel cobalt manganese (NCM 622), the diaphragm and the lithium sheet which are anode materials in a glove box protected by argon, and the electrolyte prepared in each test example is added respectively.
The statistical results of the cycle test of each battery set in the environment of 3-4.3V, 1C multiplying power charge-discharge and 60 ℃ high temperature are shown in the following table:
statistical results of battery performance tests
Figure BDA0003799099330000101
Figure BDA0003799099330000111
Example 16
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: the additive also comprises 5-acetylthiophene-2-formonitrile, and the mass ratio of the polyfluorobenzene compound to the 5-acetylthiophene-2-formonitrile is 20.
Example 17
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: the additive also comprises 1- (dimethylamino) pyrrole, and the mass ratio of the polyfluorobenzene compound to the 1- (dimethylamino) pyrrole is 10.
Example 18
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: the additive also comprises (2-allylphenoxy) trimethylsilane, and the mass ratio of the polyfluorobenzene compound to the (2-allylphenoxy) trimethylsilane is 10.
Example 19
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: the additive also comprises 4, 5-dicyano-2- (trifluoromethyl) imidazole, and the mass ratio of the polyfluorobenzene compound to the 4, 5-dicyano-2- (trifluoromethyl) imidazole is 10.
Example 20
This example provides an electrolyte, which is prepared in substantially the same manner as in example 1, except that: the additive also comprises p-toluenesulfonylmethyl isonitrile, and the mass ratio of the polyfluorobenzene compound to the p-toluenesulfonylmethyl isonitrile is 10.
Lithium-ternary nickel cobalt manganese (Li-NCM 622) battery assembly tests were performed using the electrolytes prepared in examples 1 and 16 to 20, respectively: the battery is assembled by the ternary nickel cobalt manganese (NCM 622), the diaphragm and the lithium sheet which are anode materials in a glove box protected by argon, and the electrolyte prepared in each test example is added respectively.
The statistical results of the cycle test of each battery set in the environment of 3-4.3V, 1C multiplying power charge-discharge and 60 ℃ high temperature are shown in the following table:
statistical results of battery performance tests
Electrolyte solution Storage stability Number of cycles Capacity retention rate
Example 1 Five days (clear and transparent) 100 74％
Example 16 Five days (clear and transparent) 100 86％
Example 17 Five days (clear and transparent) 100 90％
Example 18 Five days (clear and transparent) 100 89％
Example 19 Five days (clear and transparent) 100 91％
Example 20 Five days (clear and transparent) 100 92％
It should be noted that the above examples are only for further illustration and description of the technical solution of the present invention, and are not intended to further limit the technical solution of the present invention, and the method of the present invention is only a preferred embodiment and is not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A high-temperature resistant electrolyte comprises a solvent, a lithium salt and an additive, wherein the additive does not contain fluoroethylene carbonate, the additive at least contains a polyfluorobenzene compound, the mass percent of the polyfluorobenzene compound in the electrolyte is 0.1-10%, and the polyfluorobenzene compound is selected from at least one of 1, 2-difluorobenzene, 1, 3-difluorobenzene, 1, 4-difluorobenzene, 1,2, 3-trifluorobenzene, 1,2, 4-trifluorobenzene, 1,3, 5-trifluorobenzene, trifluorotoluene and trifluoromethoxybenzene;
the additive also comprises at least one of 5-acetylthiophene-2-carbonitrile, 1- (dimethylamino) pyrrole, (2-allylphenoxy) trimethylsilane, 4, 5-dicyano-2- (trifluoromethyl) imidazole and p-toluenesulfonylmethylisocyanamide which account for 1-2% by mass of the electrolyte.
2. The high temperature resistant electrolyte of claim 1 wherein the additive further comprises at least one of fluorinated carbonate, lithium nitrate, lithium fluoride, vinylene carbonate.
3. The high-temperature-resistant electrolyte as claimed in claim 1, wherein the mass ratio of the polyfluorobenzene compound to the 5-acetylthiophene-2-carbonitrile is 20.
4. The high-temperature-resistant electrolyte according to claim 1, wherein the mass ratio of the polyfluorobenzene compound to 1- (dimethylamino) pyrrole, (2-allylphenoxy) trimethylsilane, 4, 5-dicyano-2- (trifluoromethyl) imidazole or p-toluenesulfonylmethylisocyanate is 10.
5. The electrolyte as claimed in any one of claims 1 to 4, wherein the solvent is at least one selected from the group consisting of ether-based organic solvents, ester-based organic solvents, and ether-ester mixed organic solvents.
6. Use of a high temperature resistant electrolyte as claimed in any one of claims 1 to 5 in the manufacture of a secondary battery.
7. A high-temperature-resistant secondary battery comprising a positive electrode material, a negative electrode material, a separator, and the high-temperature-resistant electrolyte solution according to any one of claims 1 to 5.
8. The high-temperature resistant secondary battery as claimed in claim 7, wherein the positive electrode material is selected from one or more of lithium iron phosphate, lithium cobaltate, lithium titanate, lithium manganate, ternary nickel cobalt manganese, ternary nickel cobalt aluminum.
9. The high-temperature-resistant secondary battery according to claim 7, wherein the negative electrode material is at least one selected from graphite, a silicon negative electrode, and a metal negative electrode.
CN202210978186.2A 2022-08-16 2022-08-16 High-temperature-resistant electrolyte, secondary battery and application thereof Pending CN115425292A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116231090A (en) * 2023-05-06 2023-06-06 华中科技大学 High-pressure-resistant flame-retardant electrolyte compatible with graphite and lithium ion battery
CN116505079A (en) * 2023-06-13 2023-07-28 福州大学 Electrolyte for metal lithium secondary battery, preparation method of electrolyte and metal lithium secondary battery

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140071549A (en) * 2012-11-23 2014-06-12 주식회사 엘지화학 Electrolyte Solution for Lithium Secondary Battery and Lithium Secondary Battery Comprising The Same
CN110176631A (en) * 2019-06-12 2019-08-27 广州天赐高新材料股份有限公司 A kind of lithium secondary cell electrolyte and lithium secondary battery reducing the internal resistance of cell
KR20190142670A (en) * 2018-06-18 2019-12-27 주식회사 엘지화학 Electrolyte for lithium secondary battery and lithium secondary battery comprising the same
KR20210026499A (en) * 2019-08-30 2021-03-10 주식회사 엘지화학 Electrolyte for lithium secondary battery and lithium secondary battery comprising the same
WO2021208955A1 (en) * 2020-04-14 2021-10-21 华为技术有限公司 Electrolyte additive, secondary battery electrolyte, secondary battery and terminal
WO2021213132A1 (en) * 2020-04-22 2021-10-28 浙江大学 Lithium metal battery electrolyte containing composite additive, and preparation method therefor
CN113614974A (en) * 2018-11-09 2021-11-05 株式会社Lg新能源 Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same
CN114024024A (en) * 2021-11-04 2022-02-08 安徽工业大学 Electrolyte additive, application thereof and lithium metal battery
CN114361587A (en) * 2021-09-18 2022-04-15 华中科技大学 Local high-concentration electrolyte additive for lithium metal secondary battery and application

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140071549A (en) * 2012-11-23 2014-06-12 주식회사 엘지화학 Electrolyte Solution for Lithium Secondary Battery and Lithium Secondary Battery Comprising The Same
KR20190142670A (en) * 2018-06-18 2019-12-27 주식회사 엘지화학 Electrolyte for lithium secondary battery and lithium secondary battery comprising the same
CN113614974A (en) * 2018-11-09 2021-11-05 株式会社Lg新能源 Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same
CN110176631A (en) * 2019-06-12 2019-08-27 广州天赐高新材料股份有限公司 A kind of lithium secondary cell electrolyte and lithium secondary battery reducing the internal resistance of cell
KR20210026499A (en) * 2019-08-30 2021-03-10 주식회사 엘지화학 Electrolyte for lithium secondary battery and lithium secondary battery comprising the same
WO2021208955A1 (en) * 2020-04-14 2021-10-21 华为技术有限公司 Electrolyte additive, secondary battery electrolyte, secondary battery and terminal
WO2021213132A1 (en) * 2020-04-22 2021-10-28 浙江大学 Lithium metal battery electrolyte containing composite additive, and preparation method therefor
CN114361587A (en) * 2021-09-18 2022-04-15 华中科技大学 Local high-concentration electrolyte additive for lithium metal secondary battery and application
CN114024024A (en) * 2021-11-04 2022-02-08 安徽工业大学 Electrolyte additive, application thereof and lithium metal battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈永坤等: "1, 2, 3-三氟苯作为电解液添加剂的研究", 广东化工, no. 06, 31 March 2020 (2020-03-31), pages 50 - 51 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116231090A (en) * 2023-05-06 2023-06-06 华中科技大学 High-pressure-resistant flame-retardant electrolyte compatible with graphite and lithium ion battery
CN116231090B (en) * 2023-05-06 2023-08-11 华中科技大学 High-pressure-resistant flame-retardant electrolyte compatible with graphite and lithium ion battery
CN116505079A (en) * 2023-06-13 2023-07-28 福州大学 Electrolyte for metal lithium secondary battery, preparation method of electrolyte and metal lithium secondary battery

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