CN113054250A - Electrolyte and lithium ion battery - Google Patents
Electrolyte and lithium ion battery Download PDFInfo
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- CN113054250A CN113054250A CN201911371700.0A CN201911371700A CN113054250A CN 113054250 A CN113054250 A CN 113054250A CN 201911371700 A CN201911371700 A CN 201911371700A CN 113054250 A CN113054250 A CN 113054250A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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
The structural formula (II) is
The structural formula of the phosphite ester compound is shown in the specification
Description
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, and can be composed of a solvent, lithium salt and an additive.
201610218844.2 discloses an electrolyte for lithium ion battery, which is prepared by compounding fluoroethylene carbonate, saturated dinitrile compounds or unsaturated nitrile compounds and unsaturated phosphate compounds, so that the electrolyte can form an excellent SEI film on the negative electrode to stabilize the 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 electrolyte, which effectively improves the safety problem caused by the overcharge of the secondary battery by adding phosphorous acid compounds and nitrile compounds, reduces the volume expansion rate of the secondary battery during high-temperature storage, and improves the electrochemical performance of the secondary battery under high-temperature environment.
However, it is still necessary to develop more electrolytes to meet the market demand.
Disclosure of Invention
The invention aims to solve the technical problem of providing electrolyte with different additives and a lithium ion battery.
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
The structural formula (II) is
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, haloalkyl, alkenyl, alkenyloxy, haloalkenyl, alkynyl, alkynyloxy, haloalkynyl, phenyl, phenoxy, halophenyl, halogen, hydroxy, alkylhydroxy, haloalkylhydroxy, alkylcarbonyl, haloalkylcarbonyl, cyano, alkylcyano, haloalkylcyano, siloxy, silyl, halosilyl, 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 structural formula of the phosphite ester compound is shown in the specification
The outer layer of the phosphite compound in the present invention is coated with 6-CF3The 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 said thiosulfonate group-containing compound is one or more of the following structures:
preferably, the compound containing sulfo-sulfonate 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 halogens, 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 additive.
More preferably, the other additives account for 0.5-5% of the total mass of the electrolyte, and more preferably 1-3%.
Further preferably, the other additives include, but are not limited to, vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, methylene methanedisulfonate, vinyl sulfate, vinyl sulfite, 1, 3-propane sultone, 1, 3-dioxane, biphenyl, cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, m-fluorotoluene, 3, 4-difluorotoluene, 4-bromo-2-fluorobenzene 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, n-diethylamine trimethylsilane, hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, triphenyl phosphate, succinonitrile, adiponitrile, pimelonitrile, hexanetrinitrile, ethoxypentafluorotriphosphazene, lithium dioxalate borate, lithium oxalyldifluoroborate, lithium difluorophosphate, lithium difluorobisoxalato phosphate, tris (trimethylsilane) borate, tris (trimethylsilane) phosphate, or a combination of any of these.
According to a specific and preferred embodiment, the other additives are lithium difluorophosphate accounting for 0.1-1% of the total mass of the electrolyte, vinylene carbonate accounting for 0.5-2% of the total mass of the electrolyte, and vinyl sulfate accounting for 0.5-2% of the total mass of the electrolyte.
Preferably, the lithium salt is LiPF6、LiBF4、LiAsF6、LiClO4、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、Li(SO2F)2N、Li(CF3SO2)3C、Li(C6F5)4B、Li(C2F5SO2)2N、LiBF3C2F5、LiPF3(C2F5)3At least one of (1).
Preferably, the lithium salt accounts for 10-25% of the total amount of the electrolyte, and more preferably 10-15%.
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 50-85% of the total mass of the electrolyte, and more preferably 75-85%.
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 LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2And LiNixCoyMnzAl1-x-y-zO2(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 comprises a negative electrode current collector and a negative electrode material located on the surface of the negative electrode current collector, the negative electrode material comprises a negative electrode active material and a negative electrode binder, the negative electrode material can also optionally comprise a negative electrode conductive agent, the negative electrode conductive agent and the positive electrode conductive agent can be the same or different and are conductive agents commonly used in the field, the negative electrode active material and the negative electrode binder can be negative electrode active materials and negative electrode binders commonly used in the field, for example, the negative electrode active material can be metal lithium, metal oxide, lithium aluminum alloy, graphite, modified carbon material, silicon oxide thereof, and silicon 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 specification, "%" represents mass% unless otherwise specified.
Comparative example 1
The nonaqueous organic solvent comprises diethyl carbonate and methyl ethyl carbonate, and the mass ratio of the nonaqueous organic solvent to the diethyl carbonate to the methyl ethyl carbonate is 30%, 20% and 34% respectively; the lithium salt being LiPF6The 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
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 LiPF6The 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 LiPF6The 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
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 LiPF6The 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
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 LiPF6The 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
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
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 30%, 20% and 33% respectively; the lithium salt being LiPF6The 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, and the additive is vinylene carbonate accounting for hundred percent of the total mass of the electrolyteThe percentage is 1 percent, and the additive is that the percentage of the vinyl sulfate accounting for the total mass of the electrolyte is 1.0 percent. The additive is
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
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 LiPF6The 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
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
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 30%, 20% and 33% respectively; the lithium salt being LiPF6The 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
The percentage of the total mass of the electrolyte is 1.0% of the total weight of the composition. The additive is
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 being LiPF6The 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
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
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 LiPF6The 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
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
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 LiPF6The 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
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
Accounting for 1.0 percent of the total mass of the electrolyte.
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 being LiPF6The 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
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
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 30%, 20% and 33% respectively; the lithium salt being LiPF6The lithium salt accounts for 12.5 percent of the total mass fraction of the electrolyte, and the additive lithium difluorophosphate accounts for the total mass of the electrolyte0.5 percent of the amount of the electrolyte, 1 percent of vinylene carbonate accounting for the total mass of the electrolyte and 1.0 percent of vinyl sulfate accounting for the total mass of the electrolyte. The additive is
Accounting for 1.0 percent of the total mass of the electrolyte. The additive is
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 lot0.8Co0.1Mn0.1O2In 1Ah polymer pouch cells (NCM), the following properties were tested:
(1) the polymer soft package battery is subjected to charge and discharge cycles with the voltage interval of 2.75-4.2V and 2.75-4.25V at the 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 soft package battery 1C was charged to 6.3V at constant current and constant voltage, and the battery status was recorded, with the test results 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
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 (10)
1. An electrolyte comprising a lithium salt, an organic solvent and an additive, wherein: the additive comprises a thiosulfonate group-containing compound and/or a phosphite compound, which isWherein the compound containing sulfo sulfonate groups 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
The structural formula (II) is
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, haloalkyl, alkenyl, alkenyloxy, haloalkenyl, alkynyl, alkynyloxy, haloalkynyl, phenyl, phenoxy, halophenyl, halogen, hydroxy, alkylhydroxy, haloalkylhydroxy, alkylcarbonyl, haloalkylcarbonyl, cyano, alkylcyano, haloalkylcyano, siloxy, silyl, halosilyl, 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 structural formula of the phosphite ester compound is shown in the specification
2. The electrolyte of claim 1, wherein: the sulfo-sulfonate group-containing compound is one or more of the substances shown in the following structures:
3. the electrolyte of claim 1 or 2, wherein: the compound containing sulfo sulfonate groups accounts for 0.05-5% of the total mass of the electrolyte; the phosphite ester compound accounts for 0.05-5% of the total mass of the electrolyte.
4. The electrolyte of claim 1, wherein: the additive also comprises other additives, and 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 additive.
5. The electrolyte of claim 4, wherein: the other additives account for 0.5-5% of the total mass of the electrolyte.
6. The electrolyte of claim 4, wherein: the other additives are vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, methylene methanedisulfonate, vinyl sulfate, vinyl sulfite, 1, 3-propane sultone, 1, 3-dioxane, biphenyl, cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, m-fluorotoluene, 3, 4-difluorotoluene, 4-bromo-2-fluorobenzene 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, methoxide, ethanolamine, N-dicyclohexylcarbodiimide, N-diethylamine trimethylsilane, Hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, triphenyl phosphate, succinonitrile, adiponitrile, pimelonitrile, hexanetrinitrile, ethoxypentafluorotriphosphazene, lithium dioxalate borate, lithium oxalyldifluoroborate, lithium difluorophosphate, lithium difluorobis oxalato phosphate, tris (trimethylsilane) borate, tris (trimethylsilane) phosphate, or combinations thereof.
7. The electrolyte of claim 4, wherein: the other additives are lithium difluorophosphate accounting for 0.1-1% of the total mass of the electrolyte, vinylene carbonate accounting for 0.5-2% of the total mass of the electrolyte, and vinyl sulfate accounting for 0.5-2% of the total mass of the electrolyte.
8. The electrolyte of claim 1, wherein: the lithium salt is LiPF6、LiBF4、LiAsF6、LiClO4、LiCF3SO3、LiC4F9SO3、Li(CF3SO2)2N、Li(SO2F)2N、Li(CF3SO2)3C、Li(C6F5)4B、Li(C2F5SO2)2N、LiBF3C2F5、LiPF3(C2F5)3And the lithium salt accounts for 10-25% of the total amount of the electrolyte.
9. 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.
10. 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 solution according to any one of claims 1 to 9.
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