CN110620262A - High-voltage lithium ion battery flame retardant, electrolyte and battery - Google Patents

High-voltage lithium ion battery flame retardant, electrolyte and battery Download PDF

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CN110620262A
CN110620262A CN201910736206.3A CN201910736206A CN110620262A CN 110620262 A CN110620262 A CN 110620262A CN 201910736206 A CN201910736206 A CN 201910736206A CN 110620262 A CN110620262 A CN 110620262A
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ion battery
lithium ion
voltage
electrolyte
flame retardant
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詹元杰
黄学杰
武怿达
马晓威
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Songshan Lake Materials Laboratory
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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
    • 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
    • H01M10/42—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
    • 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

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  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a high-voltage lithium ion battery flame retardant, electrolyte and a battery thereof. The high-voltage lithium ion battery flame retardant provided by the invention is a perfluorinated or mostly fluorinated sulfonyl compound, has an antioxidant property, is relatively stable under high voltage, does not influence the performance of the lithium ion battery, can inhibit the chain reaction of hydroxyl radicals or hydrogen radicals, reduces the flammability of electrolyte, and simultaneously generates SO (sulfur oxide) by decomposing the flame retardant when the battery is combusted2Also can obstruct air, lead the battery to be self-extinguished, effectively improve the electrochemical and thermodynamic stability of the lithium ion battery, further improve the safety of the high-voltage lithium ion battery, and has the advantages of small addition, low cost, simple synthesis and the like, is easy to realize, is beneficial to widely pushingHas wide application.

Description

High-voltage lithium ion battery flame retardant, electrolyte and battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-voltage lithium ion battery flame retardant, electrolyte and a battery thereof.
Background
The use of traditional fossil fuels releases a large amount of carbon dioxide and harmful gases such as sulfide, nitride and dust, causing greenhouse effect and polluting the environment, and the development and utilization of renewable clean energy sources are imperative as the traditional fossil fuels are gradually exhausted. The clean energy comprises water energy, solar energy, wind energy, tidal energy, nuclear energy and the like, and belongs to renewable energy. The energy sources can be utilized in a mode of electric energy-energy in other forms-electric energy through intermediate conversion, namely, energy storage equipment is utilized, and a lithium ion battery in an energy storage device is paid much attention due to the advantages of high voltage, high energy density, long service life, high safety and the like, so that the lithium ion battery is rapidly developed in the application fields of portable electronic products, large-scale power supplies and energy storage power stations. The rapid development of the application field puts higher demands on the high power, high safety, long service life and low cost of the lithium ion battery. The high-voltage spinel lithium nickel manganese oxide has a high-voltage platform of 4.7V (Vs Li), the high working voltage can greatly reduce the BMS management cost and safety of the battery, the lithium nickel manganese oxide with a spinel structure has a three-dimensional lithium ion channel and has the advantage of high power, and meanwhile, the lithium nickel manganese oxide does not contain a rare resource Co, is low in cost and is a very good next-generation positive electrode battery material.
The safety problem of lithium ion batteries is always a concern, however, most of the current lithium ion batteries use carbonate organic electrolytes which are very easy to burn, and the batteries can be burnt and even exploded due to overcharge, overdischarge, overheating and the like. The addition of the flame retardant in the electrolyte can reduce the flammability of the electrolyte, but the common electrolyte flame retardant can be oxidized and decomposed under high pressure, thereby affecting the electrochemical performance of the lithium ion battery.
Disclosure of Invention
In view of the above-mentioned disadvantages, an object of the present invention is to provide a flame retardant for high-voltage lithium ion batteries, which does not undergo oxidative decomposition under high voltage, does not affect battery performance, and improves electrochemical stability and thermodynamic stability of the batteries.
The invention also aims to provide a high-voltage lithium ion battery electrolyte containing the high-voltage lithium ion battery flame retardant.
The invention also provides a lithium ion battery containing the high-voltage lithium ion battery electrolyte.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a high voltage lithium ion battery flame retardant is a perfluorinated or mostly fluorinated sulfonyl compound. Oxidative decomposition cannot occur in the circulating process of the high-voltage lithium battery, the circulating performance of the battery cannot be influenced, perfluoro or most of fluoro can inhibit the chain reaction of hydroxyl radicals or hydrogen radicals, the flammability of electrolyte is reduced, and when the battery burns, SO generated by decomposition of a flame retardant2Air can be blocked, the battery can be self-extinguished, the electrochemical and thermodynamic stability of the high-voltage lithium battery is improved, and the safety of the high-voltage lithium battery is further improved.
As an improvement of the invention, the degree of fluorination is 60-100%.
As an improvement of the present invention, it contains a sulfonyl functional group, the structural formula of which is shown below:
r in the structural formula1Selected from perfluorinated or partially fluorinated ester groups, phenyl groups, cyano groups, alkenyl groups and halogen atoms, R2Selected from perfluoro or partially fluoro alkyl groups having 1 to 10 carbon atoms.
As an improvement of the present invention, it is one or more selected from the group consisting of perfluoro-1-octanesulfonyl fluoride, perfluorobutylsulfonyl fluoride, N-ethylperfluoro-N-octanesulfonamide, perfluorobutylsulfonate, perfluorooctanesulfonyl chloride, perfluorophenyl 3- (pyridin-2-yldisulfonyl) propionate, perfluoro (4-methyl-3, 6-dioxoocta-7-ene) -sulfonyl fluoride, perfluorohexylsulfonyl fluoride, perfluorophenyl 4-methyl-4- (pyridin-2-yldisulfonyl) valerate, lithium fluorosulfonyldifluoroacetate, pentafluorobenzenesulfonyl chloride, 2,3,3,4, 4-hexafluoropentan-1, 5-diylbis (4-methylbenzenesulfonate).
The electrolyte of the high-voltage lithium ion battery consists of an additive, lithium salt, an organic solvent and the flame retardant of the high-voltage lithium ion battery as claimed in any one of claims 1 to 4, wherein the addition proportion of the flame retardant of the high-voltage lithium ion battery in the electrolyte of the high-voltage lithium ion battery is 0.1 to 15 percent by mass.
As a modification of the invention, the additive further comprises other functional additives selected from one or more of fluoroethylene carbonate (FEC), 1, 3-Propanediol Cyclic Sulfate (PCS), Vinylene Carbonate (VC), Ethylene Sulfite (ES), dimethyl sulfite (DMS), and trimethylsilyl phosphite.
As a modification of the invention, the organic solvent is selected from one or more of Propylene Carbonate (PC), Ethylene Carbonate (EC), Butylene Carbonate (BC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Methyl Propyl Carbonate (MPC), Dioxolane (DOL), 1, 2-Dimethoxyethane (DME), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2Me-THF), gamma-Butyrolactone (BL), Methyl Acetate (MA), Ethyl Acetate (EA), dimethyl sulfoxide (DMSO) and Sulfolane (SL) which are mixed according to any proportion.
According to the improvement of the invention, the lithium salt is one or more of lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methide, lithium bis (oxalato) borate, lithium difluoro-oxalato borate or lithium tetrafluorooxalato phosphate, and the molar concentration range of the lithium salt in the electrolyte of the high-pressure lithium ion battery is 0.5-3 mol/L.
A lithium ion battery comprising a positive electrode, a negative electrode, a separator and the high voltage lithium ion battery electrolyte of any one of claims 5 to 8.
As an improvement of the invention, the charge cut-off voltage is 4.7-5V. The positive active material of the lithium ion battery is high-voltage spinel lithium nickel manganese oxide.
The invention has the beneficial effects that: the high-voltage lithium ion battery flame retardant provided by the invention is a perfluorinated or mostly fluorinated sulfonyl compound, has an antioxidant property, is relatively stable under high voltage, does not influence the performance of the lithium ion battery, can inhibit the chain reaction of hydroxyl radicals or hydrogen radicals, reduces the flammability of electrolyte, and simultaneously burns the batterySO generated by decomposition of flame retardant during burning2The lithium ion battery can also block air, enables the battery to be self-extinguished, effectively improves the electrochemical and thermodynamic stability of the lithium ion battery, further improves the safety of the high-voltage lithium ion battery, has the advantages of small addition amount, low cost, simple synthesis and the like, is easy to realize, and is beneficial to wide popularization and application.
The present invention will be further described with reference to the following examples.
Detailed Description
Example 1:
preparing the electrolyte of the high-voltage lithium ion battery:
in a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, perfluoro-1-octane sulfonyl fluoride with the mass fraction of 3 percent is added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and the salt is stirred until the salt is completely dissolved, so that the high-voltage lithium ion battery electrolyte A1 is obtained.
Preparing a lithium ion battery:
reacting LiNi0.5Mn1.5O4(LNMO) is used as a positive electrode active material, carbon black is used as a conductive additive, carboxymethyl cellulose (CMC), a copolymer (SBR) of styrene and butadiene is used as a binder, the mixture is uniformly mixed in water according to the mass ratio of 92:5:1:2, then coated on an aluminum foil current collector, dried, cold-pressed, cut into round pieces with the diameter of phi 14mm, and placed in a glove box.
Graphite is used as a negative electrode active material, carbon black is used as a conductive additive, carboxymethyl cellulose (CMC) and a copolymer (SBR) of styrene and butadiene are used as a binder, the materials are uniformly mixed in water according to a mass ratio of 93:2:2:3, then the mixture is coated on a copper foil current collector, and after drying and cold pressing, the copper foil current collector is cut into round pieces with the diameter of phi 15mm, and the round pieces are placed in a glove box.
Polyethylene (PE) is used as a base film (12 mu m), and a nano aluminum oxide coating (2 mu m) is coated on the two sides of the base film to be used as a diaphragm.
And the positive pole piece, the diaphragm and the negative pole piece are sequentially placed, the prepared electrolyte is injected, and then the button cell with the model number of CR2032 is assembled by packaging. The prepared button cell is kept stand for 24 hours at room temperature, and then a blue battery charge and discharge tester (purchased from blue electronic corporation, Wuhan city) is adopted to perform cycle test on the cell.
Example 2:
the difference from the example 1 is the preparation of the electrolyte of the high-voltage lithium ion battery:
in a glove box filled with argon (moisture is less than 10ppm, oxygen content is less than 1ppm), ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, perfluorobutylsulfonyl fluoride with the mass fraction of 15 percent and N-ethyl perfluoro-N-octylsulfonamide with the mass fraction of 5 percent are added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and the salt is stirred until the salt is completely dissolved, so that the high-voltage lithium ion battery electrolyte A2 is obtained.
Example 3:
the difference from the example 1 is the preparation of the electrolyte of the high-voltage lithium ion battery:
in a glove box filled with argon (the water content is less than 10ppm, the oxygen content is less than 1ppm), ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, perfluorobutyl sulfonate with the mass fraction of 0.1% is added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and the salt is stirred until the salt is completely dissolved, so that the high-voltage lithium ion battery electrolyte A3 is obtained.
Example 4:
the difference from the example 1 is the preparation of the electrolyte of the high-voltage lithium ion battery:
in an argon-filled glove box (moisture is less than 10ppm, oxygen content is less than 1ppm), ethylene carbonate, ethyl methyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, perfluorooctane sulfonyl chloride with the mass fraction of 5 percent and perfluorophenyl 3- (pyridine-2-yl disulfonyl) propionate with the mass fraction of 5 percent are added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and the salt is stirred until the salt is completely dissolved, so that the high-voltage lithium ion battery electrolyte A4 is obtained.
Example 5:
the difference from the example 1 is the preparation of the electrolyte of the high-voltage lithium ion battery:
in an argon-filled glove box (moisture is less than 10ppm, oxygen content is less than 1ppm), ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, perfluoro (4-methyl-3, 6-dioxo octa-7-ene) -sulfonyl fluoride with the mass fraction of 2 percent is added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and the salt is stirred until the salt is completely dissolved, so that the high-voltage lithium ion battery electrolyte A5 is obtained.
Example 6:
the difference from the example 1 is the preparation of the electrolyte of the high-voltage lithium ion battery:
in an argon-filled glove box (moisture is less than 10ppm, oxygen content is less than 1ppm), ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, 3 mass percent of perfluorohexyl sulfonyl fluoride and 5 mass percent of perfluorophenyl 4-methyl-4- (pyridine-2-yl disulfonyl) valerate are added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and the salt is stirred until the salt is completely dissolved, so that the high-voltage lithium ion battery electrolyte A6 is obtained.
Example 7:
the difference from the example 1 is the preparation of the high-voltage lithium ion battery flame retardant:
in a glove box filled with argon (moisture is less than 10ppm, oxygen content is less than 1ppm), ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, pentafluorobenzenesulfonyl chloride with the mass fraction of 5 percent and 2,2,3,3,4, 4-hexafluoropentane-1, 5-diylbis (4-methylbenzenesulfonate) with the mass fraction of 5 percent are added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and the salt is stirred until the salt is completely dissolved, so that the high-voltage lithium ion battery electrolyte A7 is obtained.
Example 8:
the difference from the example 1 is the preparation of the high-voltage lithium ion battery flame retardant:
in a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate, ethyl methyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, and the mass components are added into the mixed solution3% perfluoro-1-octanesulfonyl fluoride, 0.5% vinylene carbonate, 2% fluoroethylene carbonate (FEC), and slowly adding lithium salt LiPF6And the concentration of the salt is 1mol/L, and the salt is stirred until the salt is completely dissolved, so that the high-voltage lithium ion battery electrolyte A8 is obtained.
Example 9:
the difference from the example 1 is the preparation of the high-voltage lithium ion battery flame retardant:
in an argon-filled glove box (moisture is less than 10ppm, oxygen content is less than 1ppm), ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, perfluoro (4-methyl-3, 6-dioxo octa-7-ene) -sulfonyl fluoride with the mass fraction of 2%, 1, 3-propanediol cyclic sulfate and 1% ethylene sulfite are added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and the solution is stirred until the salt is completely dissolved to obtain the electrolyte A9 of the lithium ion battery.
Comparative example 1:
it differs from example 1 in the preparation of the electrolyte:
in a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and stirring is carried out until the salt is completely dissolved, so as to obtain the electrolyte B1 of the lithium ion battery.
Comparative example 2:
in a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, 0.1 percent of methane sulfonyl ethyl acetate is added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and stirring is carried out until the salt is completely dissolved, so as to obtain the electrolyte B2 of the lithium ion battery.
Comparative example 3:
it differs from example 1 in the preparation of the electrolyte:
in an argon-filled glove box (moisture < 10ppm, oxygen < 1ppm), ethylene carbonate, ethyl methyl carbonate, diethyl carbonate were mixed in a mass ratio of 1:1:1Uniformly mixing the components according to the mass ratio, adding 10% of 4-acetylbenzenesulfonyl chloride into the mixed solution, and slowly adding lithium salt LiPF6And the concentration of the salt is 1mol/L, and stirring is carried out until the salt is completely dissolved, so as to obtain the electrolyte B3 of the lithium ion battery.
Comparative example 4:
in a glove box filled with argon (moisture is less than 10ppm, oxygen content is less than 1ppm), ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, tert-butyl sulfenamide with the mass fraction of 1% is added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and stirring is carried out until the salt is completely dissolved, so as to obtain the electrolyte B4 of the lithium ion battery.
Comparative example 5:
it differs from example 1 in the preparation of the electrolyte:
in a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are uniformly mixed according to the mass ratio of 1:1:1, isopropyl amine sulfonyl chloride with the mass fraction of 2 percent is added into the mixed solution, and lithium salt LiPF is slowly added6And the concentration of the salt is 1mol/L, and stirring is carried out until the salt is completely dissolved, so as to obtain the electrolyte B5 of the lithium ion battery.
Table 1 shows the results of the cycle performance test at normal temperature and high temperature of the batteries of the comparative example and the example.
TABLE 1
Battery numbering Capacity retention ratio at 100 weeks (%) Average efficiency (%)
Comparative example 1 71 99.3
Comparative example 2 55 98.2
Comparative example 3 30 97.0
Comparative example 4 50 98.1
Comparative example 5 53 98.3
Example 1 76 99.4
Example 2 75 99.3
Example 3 71 99.3
Example 4 74 99.3
Example 5 73 99.3
Example 6 75 99.4
Example 7 72 99.3
Example 8 86 98.6
Example 9 87 98.5
As can be seen from the test results of table 1:
as compared with the comparative example, when the non-fluorinated or low-fluorinated sulfonyl compound is used as the flame retardant, the flame retardant is decomposed under high pressure, the electrochemical cycle performance of the battery is seriously affected, and the efficiency and the capacity retention rate of the battery are greatly reduced, which indicates that the non-fluorinated or low-fluorinated sulfonyl compound is not suitable for being used as the flame retardant of the high-pressure lithium ion battery.
In the examples, it can be seen that when the perfluoro or partially fluoro sulfonyl compound is used as the flame retardant, the efficiency of the battery is not reduced, and the capacity retention rate of the battery can be slightly improved by the partial flame retardant additive, which indicates that the high-voltage lithium ion battery flame retardant of the invention has the effect of gaining the battery.
Table 2 compares the self-extinguishing times of the electrolytes of the comparative and examples.
TABLE 2
Electrolyte numbering Content of flame retardant (%) Self-extinguishing time (s/g)
A1 3 72
A2 15 55
A3 0.1 77
A4 10 65
A5 2 75
A6 8 66
A7 10 63
A8 3 71
A9 2 70
B1 0 83
B2 0.1 79
B3 10 73
B4 1 76
B5 2 75
As can be seen from Table 2, the self-extinguishing time of the electrolyte is remarkably reduced after the high-voltage lithium ion battery flame retardant is added, the self-extinguishing time is shorter along with the increase of the content, and when the addition amount of the high-voltage lithium ion battery flame retardant is 15%, the self-extinguishing time of the electrolyte is reduced from 83s/g to 55s/g, and is reduced by 28s/g, so that the effect is very remarkable. It can be seen from the comparative examples that when a non-fluorinated or low-fluorinated sulfonyl compound is used as a flame retardant, the self-extinguishing effect is far less than that of the high-voltage lithium ion battery flame retardant of the invention when the same amount of the sulfonyl compound is added.
The above examples are only preferred embodiments of the present invention, and the present invention is not limited to all embodiments, and any technical solution using one of the above examples or equivalent changes made according to the above examples is within the scope of the present invention.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. Other flame retardants, electrolytes and batteries prepared by the same or similar methods and compositions as described in the above examples are within the scope of the invention.

Claims (10)

1. The high-voltage lithium ion battery flame retardant is characterized in that the flame retardant is a perfluorinated or mostly fluorinated sulfonyl compound.
2. The flame retardant for the high-voltage lithium ion battery according to claim 1, wherein the degree of fluorination is 60 to 100%.
3. The high-voltage lithium ion battery flame retardant of claim 1, which contains a sulfonyl functional group, and has a structural formula shown as follows:
r in the structural formula1Selected from perfluorinated or partially fluorinated ester groups, phenyl groups, cyano groups, alkenyl groups and halogen atoms, R2Selected from perfluoro or partially fluoro alkyl groups having 1 to 10 carbon atoms.
4. The high voltage lithium ion battery flame retardant of claim 1, it is one or more selected from the group consisting of perfluoro-1-octanesulfonyl fluoride, perfluorobutylsulfonyl fluoride, N-ethylperfluoro-N-octanesulfonamide, perfluorobutylsulfonate, perfluorooctanesulfonyl chloride, perfluorophenyl 3- (pyridin-2-yldisulfonyl) propionate, perfluoro (4-methyl-3, 6-dioxaocta-7-ene) -sulfonyl fluoride, perfluorohexylsulfonyl fluoride, perfluorophenyl 4-methyl-4- (pyridin-2-yldisulfonyl) valerate, lithium fluorosulfonyldifluoroacetate, pentafluorobenzenesulfonyl chloride, 2,3,3,4, 4-hexafluoropentane-1, 5-diylbis (4-methylbenzenesulfonate).
5. The electrolyte of the high-voltage lithium ion battery is characterized by comprising an additive, a lithium salt, an organic solvent and the flame retardant of the high-voltage lithium ion battery as defined in any one of claims 1 to 4, wherein the addition ratio of the flame retardant of the high-voltage lithium ion battery in the electrolyte of the high-voltage lithium ion battery is 0.1-15% by mass.
6. The high voltage lithium ion battery electrolyte of claim 5 wherein the additives further comprise other functional additives selected from one or more of fluoroethylene carbonate, 1, 3-propanediol cyclic sulfate, vinylene carbonate, ethylene sulfite, dimethyl sulfite, (trimethylsilyl) phosphite.
7. The electrolyte of the high-voltage lithium ion battery of claim 5, wherein the organic solvent is selected from one or more of propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dioxolane, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, gamma-butyrolactone, methyl acetate, ethyl acetate, dimethyl sulfoxide and sulfolane.
8. The high-voltage lithium ion battery electrolyte according to claim 5, wherein the lithium salt is one or more of lithium tetrafluoroborate, lithium hexafluorophosphate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methide, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate and lithium tetrafluoro (oxalato) phosphate, and the molar concentration of the lithium salt in the high-voltage lithium ion battery electrolyte is in a range of 0.5 to 3 mol/L.
9. A lithium ion battery, which is characterized by comprising a positive electrode, a negative electrode, a diaphragm and the high-voltage lithium ion battery electrolyte as claimed in any one of claims 5 to 8.
10. The lithium ion battery according to claim 9, wherein the charge cut-off voltage is 4.7 to 5V.
CN201910736206.3A 2019-08-09 2019-08-09 High-voltage lithium ion battery flame retardant, electrolyte and battery Pending CN110620262A (en)

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Publication number Priority date Publication date Assignee Title
CN112331919A (en) * 2020-11-10 2021-02-05 郑州中科新兴产业技术研究院 Electrolyte suitable for silicon-carbon negative electrode material
CN113363583A (en) * 2021-06-25 2021-09-07 珠海市赛纬电子材料股份有限公司 Electrolyte additive, non-aqueous electrolyte and lithium ion battery thereof
CN118156587A (en) * 2024-03-28 2024-06-07 哈尔滨理工大学 Preparation method and application of low-temperature electrolyte for lithium metal battery

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CN109148958A (en) * 2018-10-16 2019-01-04 华南师范大学 A kind of electrolyte and its preparation method and application
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CN103633368A (en) * 2013-10-28 2014-03-12 山东海容电源材料有限公司 Flame-retardant additive for electrolyte and flame-retardant lithium ion battery electrolyte
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CN112331919A (en) * 2020-11-10 2021-02-05 郑州中科新兴产业技术研究院 Electrolyte suitable for silicon-carbon negative electrode material
CN113363583A (en) * 2021-06-25 2021-09-07 珠海市赛纬电子材料股份有限公司 Electrolyte additive, non-aqueous electrolyte and lithium ion battery thereof
CN118156587A (en) * 2024-03-28 2024-06-07 哈尔滨理工大学 Preparation method and application of low-temperature electrolyte for lithium metal battery

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