CN113054250B - Electrolyte and lithium ion battery - Google Patents

Electrolyte and lithium ion battery Download PDF

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CN113054250B
CN113054250B CN201911371700.0A CN201911371700A CN113054250B CN 113054250 B CN113054250 B CN 113054250B CN 201911371700 A CN201911371700 A CN 201911371700A CN 113054250 B CN113054250 B CN 113054250B
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electrolyte
total mass
carbonate
percent
compound
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CN113054250A (en
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陈黎
王婷婷
甘朝伦
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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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
    • 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 relates to an electrolyte, which comprises lithium salt, an organic solvent and an additive, wherein the additive comprises a sulfo-sulfonate-group-containing compound and/or a phosphite ester compound, the sulfo-sulfonate-group-containing compound is one or more of substances shown in a structural formula (I) and/or one or more of substances shown in a structural formula (II), and the structural formula (I) is
Figure DDA0002339813880000011
The structural formula (II) is
Figure DDA0002339813880000012
The structural formula of the phosphite ester compound is shown as

Description

Electrolyte and lithium ion battery
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to an electrolyte and a lithium ion battery.
Background
The electrolyte is an important component in the lithium ion battery, plays a role in conducting electrons between the positive electrode and the negative electrode of the lithium ion battery, can be composed of a solvent, lithium salt and an additive, and the comprehensive performance of the lithium ion battery is improved by screening the additive by the conventional method at present.
201610218844.2 discloses an electrolyte for lithium ion battery, which is prepared by compounding fluoroethylene carbonate, saturated dinitrile compound or unsaturated nitrile compound, and unsaturated phosphate compound to form excellent SEI film on negative electrode and stabilize negative electrode; meanwhile, a better protective film can be formed on the positive electrode to complex metal ions, so that the dissolution of the metal ions and the decomposition of electrolyte on the positive electrode are inhibited, and the high-temperature storage performance of the battery is obviously improved. In this patent, the film forming properties of phosphites on both the positive and negative electrodes are mentioned.
201711478144.8 discloses an electrolyte and a lithium ion battery using the same, wherein the electrolyte effectively improves the safety problem caused by overcharge of a secondary battery by adding a phosphorous acid compound and a nitrile compound, and simultaneously reduces the volume expansion rate of the secondary battery during high-temperature storage and improves the electrochemical performance of the secondary battery in a high-temperature environment.
However, it is still necessary to develop more electrolytes to meet the market demand.
Disclosure of Invention
The invention aims to provide electrolyte and a lithium ion battery with different additives.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention aims to provide an electrolyte, which comprises a lithium salt, an organic solvent and an additive, wherein the additive comprises a sulfo sulfonate group-containing compound and/or a phosphite ester compound, the sulfo sulfonate group-containing compound is one or more of substances shown in a structural formula (I) and/or one or more of substances shown in a structural formula (II), and the structural formula (I) is
Figure BDA0002339813870000011
The structural formula (II) is
Figure BDA0002339813870000012
Wherein, R1 is one of alkyl, alkoxy, halogenated alkyl, alkenyl, alkenyloxy, halogenated alkenyl, alkynyl, alkynyloxy, halogenated alkynyl, phenyl, phenoxy, halogenated phenyl and halogen; r2 is one of alkyl, alkoxy, halogenated alkyl, alkenyl, alkenyloxy, halogenated alkenyl, alkynyl, alkynyloxy, halogenated alkynyl, phenyl, phenoxy, halogenated phenyl, halogen, hydroxyl, alkylhydroxyl, halogenated alkylhydroxyl, alkylcarbonyl, halogenated alkylcarbonyl, cyano, alkylcyano, halogenated alkylcyano, siloxy, silyl, halogenated silyl, amino and alkylamino; a is one of alkyl, alkoxy, halogenated alkyl, alkenyl, alkenyloxy, halogenated alkenyl, phenyl, phenoxy, halogenated phenyl, halogen, a sulfur-containing group and a nitrogen-containing group; n is an integer of 1 to 10;
the above-mentionedThe structural formula of the phosphite ester compound is
Figure BDA0002339813870000021
The outer layer of the phosphite compound in the present invention is coated with 6-CF 3 The compound can be self-stabilized in the electrolyte, and the cycle performance, rate capability and safety performance of the battery are improved by adding the compound containing the sulpho-sulfonate group or the phosphite ester compound. In addition, the phosphite ester compound can cooperate with an-S-substituted-0-thiosulfonic acid compound to improve the thermal stability and the electrochemical stability of the anode and cathode protective films, so that the cycle performance, the rate capability and the safety performance of the battery are further improved.
Preferably, the thiosulfonate group-containing compound is one or more of the following structures:
Figure BDA0002339813870000022
preferably, the compound containing sulfo-ester groups accounts for 0.05-5% of the total mass of the electrolyte; more preferably 0.1 to 2%.
Preferably, the phosphite ester compound accounts for 0.05-5% of the total mass of the electrolyte; more preferably 0.1 to 2%.
Preferably, the additive also comprises other additives, and the other additives comprise but are not limited to one or more of cyclic carbonate containing double bonds, cyclic carbonate containing halogen, sulfonic ester, sultone, sulfuric ester, sulfite, benzene compound, fluorobenzene compound, nitrile compound, cyclic ether compound, phosphazene compound, phosphate ester, boron compound, amine compound, silicon-containing compound and lithium salt type additive.
More preferably, the other additive accounts for 0.5 to 5%, and still more preferably 1 to 3% of the total mass of the electrolyte.
Further preferably, the other additives include, but are not limited to, one or more of vinylene carbonate, vinyl ethylene carbonate, vinyl fluorocarbonate, methylene methanedisulfonate, vinyl sulfate, vinyl sulfite, 1, 3-propanesultone, 1, 3-dioxane, biphenyl, cyclohexylbenzene, tert-butylbenzene, tert-pentylbenzene, m-fluorotoluene, 3, 4-difluorotoluene, 4-bromo-2-fluorophenylmethyl ether, p-fluorotoluene, p-xylene, 1, 2-dimethoxy-4-nitrobenzene, diphenyl carbonate, N-phenylmaleimide, pentafluoroanisole, 2, 5-di-tert-butyl, 1, 4-dimethoxybenzene, adiponitrile, hexanetrinitrile, succinonitrile, N-butylamine, methanolamine, ethanolamine, N-dicyclohexylcarbodiimide, N-diethylamine trimethylsilane, hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, triphenylamine phosphate, succinonitrile, adiponitrile, heptanedinitrile, ethoxypentafluophosphazene, lithium diboronate, difluoroboron oxalate, lithium difluorophosphate, lithium difluorobis (lithium difluoroborate), lithium difluorotrisiliconate, lithium trisiliconate, lithium dihydrogen phosphate, or a combination of trisiliconate (lithium dihydrogen).
According to a specific and preferred embodiment, said other additives are lithium difluorophosphate in an amount of 0.1 to 1% by mass of the total mass of said electrolyte, vinylene carbonate in an amount of 0.5 to 2% by mass of the total mass of said electrolyte, and vinyl sulfate in an amount of 0.5 to 2% by mass of the total mass of said electrolyte.
Preferably, the lithium salt is LiPF 6 、LiBF 4 、LiAsF 6 、LiClO 4 、LiCF 3 SO 3 、LiC 4 F 9 SO 3 、Li(CF 3 SO 2 ) 2 N、Li(SO 2 F) 2 N、Li(CF 3 SO 2 ) 3 C、Li(C 6 F 5 ) 4 B、Li(C 2 F 5 SO 2 ) 2 N、LiBF 3 C 2 F 5 、LiPF 3 (C 2 F 5 ) 3 At least one of (1).
Preferably, the lithium salt accounts for 10% to 25% of the total amount of the electrolyte, and more preferably 10% to 15%.
Preferably, the organic solvent includes but is not limited to one or more of carbonate, carboxylate, ether, sulfone and sulfoxide, or a combination of one or more of carbonate, carboxylate, ether, sulfone and sulfoxide and one or more of fluoro carbonate, fluoro carboxylate, fluoro ether, fluoro sulfone and fluoro sulfoxide.
Further preferably, the organic solvent includes, but is not limited to, one or more of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethyl methyl carbonate, ethylene glycol dimethyl ether, r-butyrolactone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, sulfolane, methyl ethyl sulfone, dimethyl sulfoxide, fluoroethylene carbonate, difluoroethylene carbonate, trifluoroethyl carbonate, fluoroethylene sulfone, and tetrafluoroethyl tetrafluoropropyl ether.
Preferably, the organic solvent accounts for 50 to 85 percent of the total mass of the electrolyte, and more preferably 75 to 85 percent.
Another aspect of the present invention is to provide a lithium ion battery, including a casing, a cell accommodated in the casing, and a non-aqueous electrolyte, where the cell includes a positive electrode, a negative electrode, and a separator located between the positive electrode and the negative electrode, and the electrolyte is the above electrolyte.
Specifically, the positive electrode comprises a positive electrode current collector and a positive electrode material positioned on the surface of the positive electrode current collector, the positive electrode material comprises a positive electrode active substance, a positive electrode conductive agent and a positive electrode binder, and the positive electrode active substance can be LiNi x Co y Mn 1-x-y O 2 、LiNi x Co y Al 1-x-y O 2 And LiNi x Co y Mn z Al 1-x-y-z O 2 (x≥0.8，y>0，z>0). The positive electrode conductive agent is acetylene black or a carbon nano tube, and the positive electrode binder is polyvinylidene fluoride.
Specifically, the negative electrode includes a negative electrode current collector and a negative electrode material located on the surface of the negative electrode current collector, the negative electrode material includes a negative electrode active material and a negative electrode binder, the negative electrode material may also optionally include a negative electrode conductive agent, the negative electrode conductive agent may be the same as or different from the positive electrode conductive agent, and both the negative electrode conductive agent and the positive electrode conductive agent are conductive agents commonly used in the art, and the negative electrode active material and the negative electrode binder may be negative electrode active materials and negative electrode binders commonly used in the art, for example, the negative electrode active material may be metal lithium, metal oxide, lithium-aluminum alloy, graphite, modified carbon material, silicon oxide, silicon carbide, and silicon-oxygen-carbon. Preferably, the negative electrode active material is graphite.
In particular, the separator layer is a separator layer conventionally used in the art.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the electrolyte can improve the cycling stability, rate capability, safety performance and the like of the battery, and further, researches show that the phosphite ester with the structure general formula and stable combination of the thiosulfonate compound is combined with an organic solvent, a lithium salt and other additives in the non-aqueous electrolyte and optimized, so that the non-aqueous electrolyte can further improve the cycling stability, rate capability, safety performance and the like of the lithium ion battery, particularly the lithium ion battery with the high-nickel type positive electrode.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples. In this context, "%" represents mass% unless otherwise specified.
Comparative example 1
The nonaqueous organic solvent comprises diethyl carbonate and methyl ethyl carbonate, which respectively account for 30 percent, 20 percent and 34 percent of the electrolyte by mass; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounts for 1 percent of the total mass of the electrolyte, the additive is vinyl sulfate accounts for 1.0 percent of the total mass of the electrolyte, and the additive is added
Figure BDA0002339813870000051
Accounting for 1.0 percent of the total mass of the electrolyte.
Comparative example 2
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%,20% and 35% respectively; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounting for 1 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte.
Example 1
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%,20% and 34% respectively; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounting for 1 percent of the total mass of the electrolyte, the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte
Figure BDA0002339813870000052
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 2
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%,20% and 34% respectively; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounting for 1 percent of the total mass of the electrolyte, the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte
Figure BDA0002339813870000061
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 3
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%,20% and 33% respectively; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounting for 1 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000062
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000063
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 4
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is respectively 30%,20% and 33%; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounting for 1 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000071
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000072
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 5
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%,20% and 33% respectively; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte, and the additive difluorophosphoric acidLithium accounts for 0.5 percent of the total mass of the electrolyte, the additive accounts for 1 percent of vinylene carbonate and 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000073
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000074
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 6
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is respectively 30%,20% and 33%; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounting for 1 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000081
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000082
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 7
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%,20% and 33% respectively; the lithium salt is LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounts for 1 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounts for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000083
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000084
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 8
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%,20% and 33% respectively; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounting for 1 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000091
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000092
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 9
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%,20% and 33% respectively; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounting for 1 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000093
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000094
Accounts for the total mass of the electrolyteThe ratio was 1.0%.
Example 10
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is 30%,20% and 33% respectively; the lithium salt is LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounting for 1 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000101
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000102
Accounting for 1.0 percent of the total mass of the electrolyte.
Example 11
The nonaqueous organic solvent is ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the ethylene carbonate, the diethyl carbonate and the methyl ethyl carbonate to the electrolyte is respectively 30%,20% and 33%; the lithium salt being LiPF 6 The lithium salt accounts for 12.5 percent of the total mass of the electrolyte, the additive lithium difluorophosphate accounts for 0.5 percent of the total mass of the electrolyte, the additive is vinylene carbonate accounting for 1 percent of the total mass of the electrolyte, and the additive is vinyl sulfate accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000103
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Figure BDA0002339813870000104
Accounting for 1.0 percent of the total mass of the electrolyte.
Results of the experiment
The electrolytes obtained in comparative example 1 and example 1 were hermetically stored at normal temperature of 25 ℃ for 0 day, 7 days, and 30 days, respectively, and the concentration change of different kinds of phosphites in the electrolyte was measured by gas chromatography GC as shown in table 1.
TABLE 1
Day 0 7 days 30 days
Comparative example 1 phosphite concentration% 0.999 0.926 0.813
Phosphite concentration% in example 1 1.098 1.062 1.081
As can be seen from the above table, the phosphite compounds in the examples of the present invention have better stability in lithium ion electrolytes.
The electrolytes obtained in comparative example 1, comparative example 2, and examples 1 to 11 were injected into LiNi of the same lot 0.8 Co 0.1 Mn 0.1 O 2 In 1Ah polymer pouch cells (NCM), the following properties were tested:
(1) The polymer soft package battery is subjected to charge and discharge cycles with 1C voltage interval of 2.75-4.2V and 2.75-4.25V at normal temperature, and the test results are shown in table 2.
(2) After the polymer soft package battery is charged to 4.2V at the normal temperature at 0.2C, the polymer soft package battery is discharged at 1C, 2C and 5C respectively, and the test results are shown in Table 3.
(3) The polymer pouch cell 1C was charged to 6.3V at constant current and constant voltage, the state of the cell was recorded, and the test results are shown in table 4.
TABLE 2
Normal temperature 500Z Retention ratio (4.2V) Normal temperature 300Z Retention Rate (4.25V)
Comparative example 1 60.30 62.87
Comparative example 2 56.14 55.81
Example 1 66.45 69.06
Example 2 68.92 70.45
Example 3 72.76 71.14
Example 4 71.38 70.63
Example 5 73.55 70.97
Example 6 72.89 71.23
Example 7 76.09 74.29
Example 8 71.20 69.95
Example 9 72.84 71.33
Example 10 72.31 71.07
Example 11 70.80 69.78
TABLE 3
1C discharge Capacity mAh 2C discharge capacity mAh 5C discharge Capacity mAh
Comparative example 1 907.4 646.3 451.6
Comparative example 2 887.1 592.8 373.4
Example 1 939.2 653.5 476.9
Example 2 957.8 721.8 528.3
Example 3 961.0 738.1 556.7
Example 4 945.1 704.9 534.2
Example 5 939.7 697.1 515.1
Example 6 940.6 699.0 511.0
Example 7 975.2 755.0 582.5
Example 8 934.3 661.4 506.2
Example 9 937.8 728.3 516.4
Example 10 940.1 720.2 520.9
Example 11 919.3 675.8 539.4
TABLE 4
Figure BDA0002339813870000121
Figure BDA0002339813870000131
As can be seen from the above table, the examples of the present invention are superior to the batteries prepared in the comparative examples in both the cycle performance at normal temperature and the rate performance and safety performance.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (7)

1. An electrolyte comprising a lithium salt, an organic solvent and an additive, wherein: the additive comprises a sulfo sulfonate group-containing compound and a phosphite ester compound, wherein the sulfo sulfonate group-containing compound has a specific structural formula
Figure DEST_PATH_IMAGE001
、
Figure 462521DEST_PATH_IMAGE002
、
Figure DEST_PATH_IMAGE003
、
Figure 192711DEST_PATH_IMAGE004
、
Figure DEST_PATH_IMAGE005
、
Figure 300344DEST_PATH_IMAGE006
One or more than one substance shown in a structural formula (II), wherein the structural formula (II) is
Figure DEST_PATH_IMAGE007
(ii) a Wherein, R1 is one of alkyl, alkoxy, halogenated alkyl, alkenyl, alkenyloxy, halogenated alkenyl, alkynyl, alkynyloxy, halogenated alkynyl, phenyl, phenoxy, halogenated phenyl and halogen; a is one of alkyl, alkoxy, halogenated alkyl, alkenyl, alkenyloxy, halogenated alkenyl, phenyl, phenoxy, halogenated phenyl, halogen, a sulfur-containing group and a nitrogen-containing group; n is an integer of 1 to 10;
the structural formula of the phosphite ester compound is shown as
Figure 508602DEST_PATH_IMAGE008
；
The compound containing sulfo sulfonate groups accounts for 0.1 to 2 percent of the total mass of the electrolyte; the phosphite ester compound accounts for 0.1 to 2 percent of the total mass of the electrolyte;
the electrolyte solution also comprises other additives, wherein the other additives are one or a combination of more of double-bond-containing cyclic carbonate, halogen-containing cyclic carbonate, sulfonate, sultone, sulfate, sulfite, benzene compound, fluorobenzene compound, nitrile compound, cyclic ether compound, phosphazene compound, phosphate, boron compound, amine compound, silicon-containing compound and lithium salt type additives, and the other additives account for 0.5-5% of the total mass of the electrolyte solution.
2. The electrolyte of claim 1, wherein: the compound of the structural formula (II) is one or more of the substances shown in the following structures:
Figure DEST_PATH_IMAGE009
、
Figure 650871DEST_PATH_IMAGE010
、
Figure DEST_PATH_IMAGE011
。
3. the electrolyte of claim 1, wherein: the other additive is one or a combination of vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, methylene methanedisulfonate, vinyl sulfate, vinyl sulfite, 1, 3-propanesultone, 1, 3-dioxane, biphenyl, cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, m-fluorotoluene, 3, 4-difluorotoluene, 4-bromo-2-fluorophenylmethyl ether, p-fluorotoluene, p-xylene, 1, 2-dimethoxy-4-nitrobenzene, diphenyl carbonate, N-phenylmaleimide, pentafluoroanisole, 2, 5-di-tert-butyl, 1, 4-dimethoxybenzene, adiponitrile, hexanetrinitrile, succinonitrile, N-butylamine, methylamine, ethanolamine, N-dicyclohexylcarbodiimide, N-diethylamine trimethylsilane, hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, triphenyl phosphate, succinonitrile, adiponitrile, heptadinitrile, hexanetrinitrile, ethoxypentafluorotriphosphazene, lithium dioxaborate, lithium difluoroborate, lithium difluorophosphate, lithium difluorotrisilicate, lithium difluorotrisiliconate (lithium phosphate), lithium dihydrogen phosphate), or tricresyl oxalate.
4. The electrolyte of claim 1, wherein: the other additives are lithium difluorophosphate accounting for 0.1 to 1 percent of the total mass of the electrolyte, vinylene carbonate accounting for 0.5 to 2 percent of the total mass of the electrolyte, and vinyl sulfate accounting for 0.5 to 2 percent of the total mass of the electrolyte.
5. The electrolyte of claim 1, wherein: the lithium salt is LiPF 6 、LiBF 4 、LiAsF 6 、LiClO 4 、LiCF 3 SO 3 、LiC 4 F 9 SO 3 、Li(CF 3 SO 2 ) 2 N、Li (SO 2 F) 2 N、Li(CF 3 SO 2 ) 3 C、Li(C 6 F 5 ) 4 B、Li(C 2 F 5 SO 2 ) 2 N 、LiBF 3 C 2 F 5 、LiPF 3 (C 2 F 5 ) 3 And the lithium salt accounts for 10% -25% of the total amount of the electrolyte.
6. The electrolyte of claim 1, wherein: the organic solvent is one or more of carbonate, carboxylate, ether, sulfone and sulfoxide, or a combination of one or more of carbonate, carboxylate, ether, sulfone and sulfoxide and one or more of fluoro carbonate, fluoro carboxylate, fluoro ether, fluoro sulfone and fluoro sulfoxide, and accounts for 50-85% of the total mass of the electrolyte.
7. A lithium ion battery comprising a housing, a cell contained in the housing, and a non-aqueous electrolyte, wherein the cell comprises a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, the lithium ion battery comprising: the electrolyte is the electrolyte according to any one of claims 1 to 6.
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