CN111048830A - Nonaqueous electrolyte solution and lithium ion secondary battery - Google Patents

Nonaqueous electrolyte solution and lithium ion secondary battery Download PDF

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CN111048830A
CN111048830A CN201811189038.2A CN201811189038A CN111048830A CN 111048830 A CN111048830 A CN 111048830A CN 201811189038 A CN201811189038 A CN 201811189038A CN 111048830 A CN111048830 A CN 111048830A
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compound
electrolytic solution
nonaqueous electrolytic
sulfate
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CN111048830B (en
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陈洲文
邢玉金
贺伟
刘承一
董剑
文娟·刘·麦蒂斯
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Weihong Advanced Materials Co
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Microvast Power Systems Huzhou 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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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Abstract

The invention provides a nonaqueous electrolyte, which comprises at least two compounds dissolved in a solvent and a lithium salt dissolved in the solvent, wherein the two compounds comprise a compound A and a compound C, the compound A is selected from a sulfate compound, and the compound C is selected from at least one of a siloxane compound and/or a phosphite compound. The non-aqueous electrolyte is suitable for preparing a lithium ion secondary battery, and the lithium ion secondary battery using the electrolyte has better cycle performance and high-temperature storage characteristics under high and low temperature conditions.

Description

Nonaqueous electrolyte solution and lithium ion secondary battery
Technical Field
The present invention relates to a nonaqueous electrolyte solution for a lithium ion secondary battery and a lithium ion secondary battery.
Background
Compared with other batteries, the lithium ion battery has high energy density and is expected to be applied to pure electric vehicles or hybrid electric vehicles. In recent years, these new energy vehicles are popular in the market, but the new energy vehicles, especially passenger vehicles, still generally face the problem of mileage anxiety, and electric vehicles with long endurance are more popular in the market and consumers, which puts higher demands on the energy density of lithium ion batteries used by the electric vehicles. The use of positive and negative electrode materials with higher capacity density is an effective way to improve the energy density of the battery, but the stronger oxidizability or activity of the materials can cause the decomposition of the electrolyte when the materials are in contact with the electrolyte, especially the dissolution of positive transition metal ions in the electrolyte is intensified under the conditions of high-temperature circulation or high-temperature storage, and the dissolved transition metal ions can cause the crystal structure of the positive electrode material to change, so that the rapid attenuation of the capacity of the lithium ion battery and the remarkable reduction of the cycle life in the circulation process are caused, and the requirements of the automobile on the service life and the performance of the battery cannot be met.
Disclosure of Invention
An object of the present invention is to provide a nonaqueous electrolytic solution suitable for use in the production of a lithium ion secondary battery. The lithium ion secondary battery using the electrolyte has better cycle performance and high-temperature storage characteristics under high and low temperature conditions.
The invention provides a nonaqueous electrolyte, which comprises at least two compounds dissolved in a solvent and a lithium salt dissolved in the solvent, wherein the two compounds comprise a compound A and a compound C, the compound A is selected from a sulfate compound shown in a structural formula 1,
Figure BDA0001826998790000011
R1-R6each independently selected from hydrogen atom, fluorine atom, saturated or unsaturated alkyl with 1-10 carbon atoms, saturated or unsaturated fluorine-containing alkyl with 1-10 carbon atoms, saturated or unsaturated alkoxy with 1-10 carbon atoms, and saturated or unsaturated nitrile with 1-10 carbon atoms;
the compound C is at least one compound shown in a structural formula 2 and/or a structural formula 3,
Figure BDA0001826998790000021
wherein R is7-R14Each independently selected from hydrogen atom, fluorine atom, saturated or unsaturated hydrocarbon group with 1-10 carbon atoms, saturated or unsaturated fluorine-containing hydrocarbon group with 1-10 carbon atoms, and carbonA saturated or unsaturated alkoxy group having 1 to 10 atoms, wherein n is 0 to 1000;
Figure BDA0001826998790000022
wherein R is15-R17Each independently selected from saturated or unsaturated hydrocarbon group with 1-10 carbon atoms, saturated or unsaturated fluorine-containing hydrocarbon group with 1-10 carbon atoms, saturated or unsaturated alkoxy group with 1-10 carbon atoms, saturated or unsaturated phenyl group, and saturated or unsaturated benzyl group.
The invention also provides a nonaqueous electrolyte, which comprises at least three compounds dissolved in a solvent and a lithium salt dissolved in the solvent, wherein the three compounds comprise a compound A, a compound B and a compound C, the compound A is selected from a sulfate compound shown in the structural formula 1,
Figure BDA0001826998790000023
R1-R6each independently selected from hydrogen atom, fluorine atom, saturated or unsaturated alkyl with 1-10 carbon atoms, saturated or unsaturated fluorine-containing alkyl with 1-10 carbon atoms, saturated or unsaturated alkoxy with 1-10 carbon atoms, and saturated or unsaturated nitrile with 1-10 carbon atoms;
the compound B is selected from Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), vinyl sulfate (DTD), Methylene Methanedisulfonate (MMDS), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), 1, 3-Propene Sultone (PST), lithium difluorophosphate (LiPO)2F2) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium difluoro (oxalato) phosphate (LiDFOP), lithium tetrafluoro (oxalato) phosphate LiPF4C204At least one of lithium bistrifluoromethylsulfonyl imide (LiTFSI) and lithium bistrifluorosulfonimide (LiFSI);
the compound C is at least one compound shown in a structural formula 2 and/or a structural formula 3,
Figure BDA0001826998790000031
wherein R is7-R14Each independently selected from hydrogen atom, fluorine atom, saturated or unsaturated alkyl with 1-10 carbon atoms, saturated or unsaturated fluorine-containing alkyl with 1-10 carbon atoms, saturated or unsaturated alkoxy with 1-10 carbon atoms, and n is 0-1000;
Figure BDA0001826998790000032
wherein R is15-R17Each independently selected from saturated or unsaturated hydrocarbon group with 1-10 carbon atoms, saturated or unsaturated fluorine-containing hydrocarbon group with 1-10 carbon atoms, saturated or unsaturated alkoxy group with 1-10 carbon atoms, saturated or unsaturated phenyl group, and saturated or unsaturated benzyl group.
According to one embodiment of the present invention, compound a is selected from at least one of bis (trimethylsilyl) sulfate, bis (dimethylvinylsilyl) sulfate, bis (triethylsilyl) sulfate and bis (diethylvinylsilyl) sulfate.
The content of the compound A in the nonaqueous electrolytic solution is 0.1 wt% to 10 wt%, and the content of the compound A in the nonaqueous electrolytic solution is preferably 0.5 wt% to 5 wt%.
According to one embodiment of the invention, compound B is selected from Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), vinyl sulfate (DTD), Methylene Methanedisulfonate (MMDS), 1, 3-Propanesultone (PS), lithium difluorophosphate (LiPO)2F2) Lithium difluorooxalato borate (LiDFOB), and lithium bis (fluorosulfonylimide) (LiFSI).
The content of the compound B in the nonaqueous electrolytic solution is 0.1 wt% to 20 wt%, and the content of the compound B in the nonaqueous electrolytic solution is preferably 0.5 wt% to 8 wt%.
According to one embodiment of the present invention, compound C includes a siloxane compound represented by formula 2 and/or a phosphite compound represented by formula 3. The phosphorous atom in the phosphite ester compound contains lone pair electrons, and can be combined with hydrogen fluoride or protons in water, and the phosphite ester can easily react with oxygen in the electrolyte to form phosphate ester so as to remove oxygen active groups; the siloxane bonds in the siloxane compound may react with hydrogen fluoride to form Si-F bonds.
For example, the siloxane compound represented by formula 2 may be selected from hexamethyldisiloxane, hexaethyldisiloxane, and tetramethyldivinyldisiloxane. The phosphite compound of formula 3 may be selected from tributyl phosphite and triphenyl phosphite.
The content of the compound C in the nonaqueous electrolytic solution is 0.01 wt% to 2 wt%, and the content of the compound C in the nonaqueous electrolytic solution is preferably 0.05 wt% to 1 wt%.
In the present invention, compound A is an essential component, which can be used together with compound C to produce a synergistic effect. The compound a introduces a sulfonate ion-containing SEI film, which is relatively thin and has low resistance, on the surface of an electrode of a lithium ion secondary battery, but has a disadvantage in that the compound a is unstable to water or acid in an electrolyte. The presence of the compound C is advantageous for removing water, acid and/or oxygen-containing active groups in the nonaqueous electrolytic solution, thereby enabling the compound A to be more stable. The inclusion of both compound a and compound C in the nonaqueous electrolyte solution can form a more stable low-resistance SEI film on the surface of the electrode of a lithium secondary battery, so that better low-temperature cycle performance can be obtained.
Further, the non-aqueous electrolyte contains the compound A, the compound B and the compound C, so that a uniform and compact SEI film with good thermal stability can be formed on the surface of the electrode of the lithium ion secondary battery, the gas generation of the lithium ion secondary battery at high temperature is reduced, and the deterioration of the high-temperature storage and high-temperature cycle performance of the lithium ion secondary battery is restrained. The synergistic effect of the compound A, the compound B and the compound C can improve the lithium ion conducting property of the SEI film, and a lithium ion secondary battery using the non-aqueous electrolyte has more excellent low-temperature cycle performance.
Examples of the nonaqueous electrolytic solution including the compound a, the compound B, and the compound C are as follows: the compound A is bis (trimethylsilyl) sulfate, and the compound B is Vinylene Carbonate (VC), 1, 3-Propane Sultone (PS) or lithium difluorophosphate(LiPO2F2) And the compound C is hexamethyldisiloxane.
Another example of the nonaqueous electrolytic solution including the compound a, the compound B, and the compound C is as follows: the compound A is bis (trimethyl silicon) sulfate, the compound B is lithium bis (fluorosulfonyl) imide (LiFSI), and the compound C is triphenyl phosphite.
Still another example of the nonaqueous electrolytic solution containing compound a, compound B, and compound C is: the compound A is bis (dimethylvinylsiloxane) sulfate, the compound B is Vinylene Carbonate (VC), and the compound C is hexamethyldisiloxane or tetramethyldivinyldisiloxane.
In the present invention, the solvent of the nonaqueous electrolytic solution is a cyclic ester and/or a chain ester.
The cyclic ester is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate and gamma-butyrolactone.
The chain ester is at least one selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, ethyl propyl carbonate, propyl acetate, methyl acetate, ethyl propionate and propyl propionate.
In the present invention, the molar concentration of the lithium salt in the solvent is 0.6 to 1.5 mol/L. The lithium salt is selected from LiPF6、LiBF4、LiAsF6、LiClO4At least one of (1).
It is another object of the present invention to provide a lithium ion secondary battery having excellent high and low temperature charge-discharge cycles and high temperature storage properties, which contains the nonaqueous electrolytic solution as described above.
The lithium ion secondary battery includes a positive electrode, a negative electrode, a separator, and the nonaqueous electrolytic solution described above.
The active material of the positive electrode is selected from lithium salts of transition metal oxides, including LiCoO2，LiMn2O4，LiNiO2，Li(Ni1-x-yCoxAly)O2，Li(Ni1-x-yCoxMny)O2And LiFePO4One or more of the components (A) and (B),wherein 0<x<1，0<y<1. The active material of the negative electrode is selected from carbon materials (including graphite, soft carbon, hard carbon, graphene, amorphous carbon and the like), silicon-containing composite materials, tin-containing composite materials, metallic lithium, lithium alloy or lithium titanate. The separator is selected from a coated or uncoated PE separator, a coated or uncoated PP separator or an aramid separator.
The structure of the secondary battery is not limited, and the secondary battery can be a button battery, a cylindrical battery, a square battery or a soft package battery packaged by an aluminum plastic film.
Detailed Description
The invention will be further illustrated with reference to the following non-limiting examples.
Preparing a lithium ion secondary battery:
preparing a positive electrode: in a mixing vessel, 95 wt% Li (Ni) was added with N-methyl-2-pyrrolidone (NMP) as a solvent0.8Mn0.1Co0.1)O2And uniformly mixing the ternary material, 3 wt% of acetylene black and 2 wt% of polyvinylidene fluoride (PVDF) to obtain positive electrode slurry, uniformly coating the positive electrode slurry on an aluminum foil, and then drying and rolling to obtain the positive electrode sheet.
Preparing a negative electrode: uniformly mixing 95 wt% of artificial graphite, 2 wt% of acetylene black, 2 wt% of styrene butadiene rubber and 1 wt% of sodium carboxymethylcellulose by using deionized water as a solvent to obtain negative electrode slurry, uniformly coating the negative electrode slurry on copper foil, and then drying and rolling to obtain a negative electrode sheet.
Preparing electrolyte: the electrolyte used by the invention is prepared in a glove box, the glove box is filled with argon with the purity of 99.999 percent, the moisture is controlled to be below 5ppm, and a certain amount of EC and EMC are mixed according to the weight ratio of 3: 7, mixing evenly, and then respectively adding LiPF6And compound A, compound B and/or compound C shown in the following examples and comparative examples to obtain LiPF6A nonaqueous electrolyte solution of a lithium ion secondary battery with a concentration of lmol/L, wherein the compound A is prepared by adopting a synthesis method disclosed by W.Patnode et al (J.Am.chem.Soc.,67,2272,1945).
The positive electrode, the PE diaphragm and the negative electrode are sequentially stacked and packaged by using an aluminum plastic film to obtain a dry battery cell, then electrolyte prepared according to the additive proportion of examples 1-13 and comparative examples 1-24 is respectively injected, and the soft package lithium ion secondary battery for performance test is obtained through the steps of standing, formation, capacity grading and the like.
And (3) testing the battery:
the electrolytes prepared according to the examples of the present invention and the comparative examples were subjected to a performance test with Li (Ni) after being assembled into a battery0.8Mn0.1Co0.1)O2The soft package battery is made of a 1Ah flexible package battery by adopting a PE diaphragm, after electrolyte is injected, the soft package battery is aged for 12h at normal temperature, and then the capacity retention rate of the soft package battery is tested at 55 ℃ for 300 weeks under 2C circulation, and the capacity retention rate, the capacity recovery rate and the low-temperature circulation capacity retention rate after the soft package battery is stored for 7 days at 70 ℃. The specific test method is as follows:
(1) capacity retention rate of 300 weeks after 2C circulation at 55 ℃ shows the high-temperature cycle performance of the battery: at 55 ℃, the formed battery is charged to 4.25V by using a 2C constant current and constant voltage, the cut-off current is 0.01C, and then the battery is discharged to 3.0V by using a 2C constant current, and the cycle is repeated for 300 weeks. The capacity retention rate calculation formula is as follows:
the 55 ℃ cycle capacity retention (%) was (300 th cycle discharge capacity/1 st cycle discharge capacity) × 100%.
(2) The method for testing the capacity retention rate and the capacity recovery rate after 7 days of storage at 70 ℃ comprises the following steps: charging the formed battery to 4.25V at normal temperature by using a 1C constant current and a constant voltage, stopping the current to 0.01C, then discharging the battery to 3.0V at the 1C constant current, and measuring the initial discharge capacity of the battery; charging to 4.25V at normal temperature with 1C constant current and constant voltage, stopping current at 0.01C, storing at 70 deg.C for 7 days, discharging at normal temperature with 1C constant current to 3.0V, and measuring the holding capacity of the battery; and then, the current is cut off to 0.01C by using a 1C constant current and a constant voltage at normal temperature, and then, the current is discharged to 3.0V by using a 1C current and a constant current, and the recovery capacity is measured. The calculation formula is as follows:
battery capacity retention (%) retention capacity/initial capacity × 100%
The battery capacity recovery ratio (%) — recovery capacity/initial capacity × 100%.
(3) The low-temperature cycle performance test method comprises the following steps: and (3) charging the formed battery to 4.25V at a constant current and a constant voltage of 1C at 25 ℃, then charging at a constant voltage until the current is reduced to 0.01C, then discharging to 3.0V at a constant current of 1C, and recording the discharge capacity at normal temperature. And then charging the battery at the normal temperature for 4.25V at a constant current of 1C, then charging the battery at a constant voltage until the current is reduced to 0.01C, placing the charged battery in an environment at the temperature of minus 10 ℃ for standing for 12 hours, keeping the temperature of minus 10 ℃ to discharge the battery to 3.0V at a constant current of 0.33C, continuing to charge the battery at the temperature of minus 10 ℃ to 4.25V at a constant current and a constant voltage of 0.33C, and repeating the steps for 200 weeks, wherein the capacity retention rate is calculated as follows.
Cycle capacity retention (%) at-10 ℃ ═ 100% (cycle discharge capacity at 200 th week/cycle discharge capacity at 1 st week).
In the embodiment of the invention, the percentages are mass percentages.
Examples 1-2 and comparative examples 1-6
Names and contents of the compound a, the compound B and/or the compound C contained in examples 1 to 2 and comparative examples 1 to 6 are shown in table 1, and results of battery tests are shown in table 2.
TABLE 1
Additive A and content Additive B and content Additive C and content
Example 1 Bis (trimethylsilyl) sulfate 2% VC 1％ 0.1% hexamethyldisiloxane
Example 2 Bis (trimethylsilyl) sulfate 2% — 0.1% hexamethyldisiloxane
Comparative example 1 — — 0.1% hexamethyldisiloxane
Comparative example 2 — — 0.1% tributyl phosphite
Comparative example 3 Bis (trimethylsilyl) sulfate 2% —
Comparative example 4 Bis (trimethylsilyl) sulfate 2% VC 1％ —
Comparative example 5 — VC 1％
Comparative example 6 — — —
TABLE 2
Figure BDA0001826998790000071
Comparing the above results, it is seen that examples 1 to 2 using compound a and compound C in combination significantly improve the capacity retention rate after the low temperature cycle test as compared with comparative example 3 using compound a alone as an additive, and that in comparative examples 1, 2 and 5 using compound C or compound B alone as an additive without using compound a in combination, the capacity retention rate and recovery rate after high temperature storage and the high temperature cycle capacity retention rate deteriorate and the low temperature cycle capacity retention rate also becomes low.
Further, when the additive a, the additive B and the additive C are used in combination, the high and low temperature cycle performance and the high temperature storage performance are more excellent than those of example 2 in which the compound a and the compound C are combined and comparative examples 1 to 3 and 5 in which the compound a, the compound B and the compound C are independently used as additives.
Examples 3 to 15
The names and contents of the compound a, the compound B and/or the compound C contained in examples 3 to 15 are shown in table 3, and the battery test results are shown in table 4.
TABLE 3
Additive A and content Additive B and content Additive C and content
Example 3 Bis (trimethylsilyl) sulfate 2% FEC 1％ 0.1% hexamethyldisiloxane
Example 4 Bis (trimethylsilyl) sulfate 2% LiPO2F2 1％ 0.1% hexamethyldisiloxane
Example 5 Bis (trimethylsilyl) sulfate 2% LiDFOP 1％ 0.1% hexamethyldisiloxane
Example 6 Bis (trimethylsilyl) sulfate 2% PS 1％ 0.1% hexamethyldisiloxane
Example 7 Bis (trimethylsilyl) sulfate 2% MMDS 1％ 0.1% tributyl phosphite
Example 8 Bis (trimethylsilyl) sulfate 2% LiFSI 1％ 0.1% tributyl phosphite
Example 9 Bis (trimethylsilyl) sulfate 2% DFOP 5％+VC 5％ 0.1% hexamethyldisiloxane
Example 10 Bis (trimethylsilyl) sulfate 2% FEC 8％+VC 5％ 0.1% hexamethyldisiloxane
Example 11 Bis (trimethylsilyl) sulfate 2% FEC 12％ 0.1% hexamethyldisiloxane
Example 12 Bis (trimethylsilyl) sulfate 2% FEC 0.1％ 0.1% hexamethyldisiloxane
Example 13 Bis (trimethylsilyl) sulfate 2% DFOP 0.1％ 0.1% hexamethyldisiloxane
Example 14 Bis (trimethylsilyl) sulfate 2% VC 0.1％ 0.1% hexamethyldisiloxane
Example 15 Bis (trimethylsilyl) sulfate 2% DTD 0.1％ 0.1% hexamethyldisiloxane
TABLE 4
Figure BDA0001826998790000081
Figure BDA0001826998790000091
Examples 16 to 17 and comparative examples 7 to 8
Names and contents of the compound a, the compound B and/or the compound C contained in examples 16 to 17 and comparative examples 7 to 8 are shown in table 5, and results of battery tests are shown in table 6.
TABLE 5
Additive A and content Additive B and content Additive C and content
Example 16 0.1 percent of bis (trimethyl silicon) sulfate VC 1％ 0.1% hexamethyldisiloxane
Example 17 Bis (trimethylsilyl) sulfate 10% VC 1％ 0.1% hexamethyldisiloxane
Comparative example 7 - VC 1％ 0.1% hexamethyldisiloxane
Comparative example 8 — VC 1％ 0.1% tributyl phosphite
TABLE 6
Figure BDA0001826998790000092
Examples 18 to 29
The names and contents of compound a, compound B and/or compound C contained in examples 18 to 29 are shown in table 7, and the results of the battery test are shown in table 8.
TABLE 7
Additive A and content Additive B and content Additive C and content
Example 18 Bis (trimethylsilyl) sulfate 2% VC 1％ 0.1% of tetramethyldivinyldisiloxane
Example 19 Bis (trimethylsilyl) sulfate 2% VC 1％ 0.1% tributyl phosphite
Example 20 Bis (trimethylsilyl) sulfate 2% VC 1％ 0.01% of tetramethyldivinyldisiloxane
Example 21 Bis (trimethylsilyl) sulfate 2% VC 1％ 2% Tetramethyldiethyldisiloxane
Example 22 Bis (trimethylsilyl) sulfate 2% VC 1％ 0.01% tributyl phosphite
Example 23 Bis (trimethylsilyl) sulfate 2% VC 1％ 2% tributyl phosphite
Example 24 Bis (trimethylsilyl) sulfate 2% VC 1％ 0.01% hexamethyldisiloxane
Example 25 Bis (trimethylsilyl) sulfate 2% VC 1％ 2% hexamethyldisiloxane
Example 26 Bis (trimethylsilyl) sulfate 2% VC 1％ 0.01% Triphenyl phosphite
Example 27 Bis (trimethylsilyl) sulfate 2% VC 1％ 2% Triphenyl phosphite
Example 28 Bis (trimethylsilyl) sulfate 2% VC 1％ 0.01% hexaethyldisiloxane
Example 29 Bis (trimethylsilyl) sulfate 2% VC 1％ 2% hexaethyldisiloxane
TABLE 8
Figure BDA0001826998790000101
As is clear from examples 3 to 29 above, by using compound a, compound B and compound C in combination in a specific concentration range, improvement in the cycle capacity retention rate at high and low temperatures and improvement in the storage performance at high temperatures can be achieved as compared with the case where compound a, compound B or compound C is used alone.
Examples 30 to 33
The names and contents of compound a, compound B and/or compound C contained in examples 30 to 33 are shown in table 9, and the results of battery tests are shown in table 10.
TABLE 9
Additive A and content Additive B and content Additive C and content
Example 30 Bis (dimethylvinylsilicone) sulfate 2% VC 1％ 0.1% hexamethyldisiloxane
Example 31 Bis (triethylsilane) sulfate 2% VC 1％ 0.1% hexamethyldisiloxane
Example 32 Bis (diethylvinylsilyl) sulfate 2% VC 1％ 0.1% hexamethyldisiloxane
Example 33 Bis (dimethylvinylsilicone) sulfate 2% VC 1％ 0.1% of tetramethyldivinyldisiloxane
Watch 10
Figure BDA0001826998790000111
Although the present invention has been described with reference to the preferred embodiments, it is to be understood that the present invention is not limited to the details of the foregoing description, and that various changes, modifications, equivalents and alterations may be made therein without departing from the spirit and scope of the invention.

Claims (12)

1. A non-aqueous electrolyte comprises at least two compounds dissolved in a solvent and a lithium salt dissolved in the solvent, wherein the two compounds comprise a compound A and a compound C, wherein the compound A is selected from a sulfate compound shown in a structural formula 1,
Figure FDA0001826998780000011
R1-R6each independently selected from hydrogen atom, fluorine atom, saturated or unsaturated alkyl with 1-10 carbon atoms, saturated or unsaturated fluorine-containing alkyl with 1-10 carbon atoms, saturated or unsaturated alkoxy with 1-10 carbon atoms, and saturated or unsaturated nitrile with 1-10 carbon atoms;
the compound C is at least one compound shown in a structural formula 2 and/or a structural formula 3,
Figure FDA0001826998780000012
wherein R is7-R14Each independently selected from hydrogen atom, fluorine atom, saturated or unsaturated alkyl with 1-10 carbon atoms, saturated or unsaturated fluorine-containing alkyl with 1-10 carbon atoms, saturated or unsaturated alkoxy with 1-10 carbon atoms, and n is 0-1000;
Figure FDA0001826998780000013
wherein R is15-R17Each independently selected from saturated or unsaturated hydrocarbon group with 1-10 carbon atoms, saturated or unsaturated fluorine-containing hydrocarbon group with 1-10 carbon atoms, saturated or unsaturated alkoxy group with 1-10 carbon atoms, saturated or unsaturated phenyl group, and saturated or unsaturated benzyl group.
2. The nonaqueous electrolytic solution of claim 1, comprising at least two or three compounds dissolved in a solvent, and a lithium salt dissolved in a solvent, the three compounds including a compound A, a compound B and a compound C, the compound B being selected from the group consisting of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), vinyl sulfate (DTD), Methylene Methanedisulfonate (MMDS), 1, 3-Propanesultone (PS), 1, 4-Butanesultone (BS), 1, 3-Propanesultone (PST), lithium difluorophosphate (LiPO)2F2) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (lidob), lithium difluoro (oxalato) phosphate (LiDF)OP), lithium tetrafluoro monooxalate phosphate (LiPF)4C204) Lithium bistrifluoromethylsulfonyl imide (LiTFSI) and lithium bistrifluorosulfonimide (LiFSI).
3. The nonaqueous electrolytic solution of claim 1 or 2, wherein the content of the compound a in the nonaqueous electrolytic solution is 0.1 wt% to 10 wt%, and preferably the content of the compound a in the nonaqueous electrolytic solution is 0.5 wt% to 5 wt%.
4. The nonaqueous electrolytic solution of claim 1 or 2, wherein the compound a is at least one selected from bis (trimethylsilyl) sulfate, bis (dimethylvinylsilyl) sulfate, bis (triethylsilyl) sulfate and bis (diethylvinylsilyl) sulfate.
5. The nonaqueous electrolytic solution of claim 1 or 2, wherein the content of the compound C in the nonaqueous electrolytic solution is 0.01 wt% to 2 wt%, and preferably the content of the compound C in the nonaqueous electrolytic solution is 0.05 wt% to 1 wt%.
6. The nonaqueous electrolytic solution of claim 1 or 2, wherein the siloxane compound represented by the structural formula 2 is selected from hexamethyldisiloxane, hexaethyldisiloxane, and tetramethyldivinyldisiloxane; the phosphite compound shown in the structural formula 3 is selected from tributyl phosphite and triphenyl phosphite.
7. The nonaqueous electrolytic solution of claim 2, wherein the content of the compound B in the nonaqueous electrolytic solution is 0.1 wt% to 20 wt%, and preferably the content of the compound B in the nonaqueous electrolytic solution is 0.5 wt% to 8 wt%.
8. The nonaqueous electrolytic solution of claim 2, wherein the compound B is selected from Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), vinyl sulfate (DTD), Methylene Methanedisulfonate (MMDS), 1, 3-Propane Sultone (PS), difluorophosphoric acidLithium (LiPO)2F2) Lithium difluorooxalato borate (LiDFOB), and lithium bis (fluorosulfonylimide) (LiFSI).
9. The nonaqueous electrolytic solution of claim 2, wherein the compound A is bis (trimethylsilyl) sulfate, and the compound B is Vinylene Carbonate (VC), 1, 3-Propane Sultone (PS), or lithium difluorophosphate (LiPO)2F2) And the compound C is hexamethyldisiloxane.
10. The nonaqueous electrolytic solution of claim 2, wherein the compound a is bis (trimethylsilyl) sulfate, the compound B is lithium bis (fluorosulfonylimide) (LiFSI), and the compound C is triphenyl phosphite.
11. The nonaqueous electrolytic solution of claim 2, wherein the compound a is bis (dimethylvinylsilyl) sulfate, the compound B is Vinylene Carbonate (VC), and the compound C is hexamethyldisiloxane or tetramethyldivinyldisiloxane.
12. A lithium ion secondary battery comprising a positive electrode, a negative electrode, a separator and the nonaqueous electrolytic solution according to any one of claims 1 to 11.
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