CN107871889A - Electrolyte solution and secondary battery - Google Patents
Electrolyte solution and secondary battery Download PDFInfo
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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
- H01M10/05—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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- 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
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- 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 an electrolyte and a secondary battery. The electrolyte includes an electrolyte salt, an organic solvent, and an additive. The additive comprises a cyclotriphosphazene compound and ethylene carbonate. When the electrolyte is applied to a secondary battery, the normal-temperature cycle performance, the high-temperature storage performance and the high-temperature thermal stability of the secondary battery can be improved at the same time.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an electrolyte and a secondary battery.
Background
The secondary battery, especially the lithium ion secondary battery, has the characteristics of high energy density, long cycle life, no pollution and the like, so that the secondary battery has wide application prospect in consumer electronics, power automobile batteries and energy storage power supplies.
In any application field, higher requirements are put on the cruising ability of the lithium ion secondary battery. In order to improve the energy density of the lithium ion secondary battery, it is one of effective approaches to develop a positive active material having a high specific capacity. At present, the transition metal oxide positive active material is a research hotspot because the theoretical specific capacity of the transition metal oxide positive active material is higher than that of other positive active materials. However, the transition metal oxide positive electrode active material has strong oxidation property in a high SOC state, which causes an electrochemical oxidation reaction of the electrolyte on the surface of the positive electrode, and causes a structural change of the transition metal oxide positive electrode active material, and causes a reduction reaction of the transition metal such as nickel, cobalt, and manganese to be eluted, thereby causing deterioration of the electrochemical performance of the lithium ion secondary battery. Therefore, it is very critical to develop an electrolyte compatible with the transition metal oxide positive active material.
Disclosure of Invention
In view of the problems of the background art, an object of the present invention is to provide an electrolyte and a secondary battery, which can simultaneously improve normal temperature cycle performance, high temperature storage performance, and high temperature thermal stability of the secondary battery when applied to the secondary battery.
In order to achieve the above object, in one aspect of the present invention, there is provided an electrolyte solution including an electrolyte salt, an organic solvent, and an additive. The additive comprises a cyclotriphosphazene compound and ethylene carbonate.
In another aspect of the present invention, the present invention provides a secondary battery including the electrolyte according to one aspect of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
the electrolyte simultaneously contains the cyclotriphosphazene compound and the ethylene carbonate, and when the electrolyte is applied to a secondary battery, the normal-temperature cycle performance, the high-temperature storage performance and the high-temperature thermal stability of the secondary battery can be simultaneously improved.
Detailed Description
The electrolyte and the secondary battery according to the present invention will be described in detail below.
First, the electrolytic solution according to the first aspect of the invention is explained.
The electrolytic solution according to the first aspect of the invention includes an electrolyte salt, an organic solvent, and an additive. The additive includes a cyclotriphosphazene compound and ethylene carbonate (VEC).
In the electrolytic solution according to the first aspect of the invention, the cyclotriphosphazene compound refers to a six-membered cyclic compound formed by alternating P and N through a single double bond and a substituted derivative thereof.
In the electrolyte according to the first aspect of the present invention, the ethylene carbonate may form a network passivation film on the surface of the positive electrode active material, which effectively inhibits the oxidation of the positive electrode active material to the electrolyte, but the ethylene carbonate easily forms a solid electrolyte interface film with high impedance on the surface of the negative electrode, which affects the performance of the secondary battery. And polyphosphate components generated by decomposition of the cyclotriphosphazene compound can be embedded in the solid electrolyte interface film formed on the surface of the negative electrode by the ethylene carbonate, so that the impedance of the solid electrolyte interface film formed on the surface of the negative electrode by the ethylene carbonate is effectively reduced. In addition, the cyclotriphosphazene compound can also absorb hydrofluoric acid in the electrolyte, and the corrosion of the hydrofluoric acid on the anode and cathode passivation film is reduced. Therefore, when the electrolyte contains the cyclotriphosphazene compound and the ethylene carbonate, a stable passive film can be formed on the surfaces of the positive electrode and the negative electrode, and the solid electrolyte interface film on the surface of the negative electrode has lower impedance and better ion transmission characteristic, so that the normal-temperature cycle performance, the high-temperature storage performance and the high-temperature thermal stability of the secondary battery are obviously improved.
In the electrolyte according to the first aspect of the present invention, the cyclotriphosphazene compound is one or more compounds selected from compounds represented by formula 1. Wherein R is1、R2、R3、R4、R5、R6Each independently selected from one of H, F, Cl, Br, I, C1-20 alkyl, C1-20 halogenated alkyl, C2-20 alkenyl, C2-20 halogenated alkenyl, C6-26 aryl, C6-26 halogenated aryl, C1-20 alkoxy, C1-20 halogenated alkoxy, C6-26 aryloxy and C6-26 halogenated aryloxy; r1、R3、R5At least one of them is selected from C1-20 alkaneOne of a hydrocarbon group, a halogenated alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a halogenated alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 26 carbon atoms, a halogenated aryl group having 6 to 26 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 26 carbon atoms, and a halogenated aryloxy group having 6 to 26 carbon atoms; r2、R4、R6At least two of (a) are each independently selected from one of F, Cl, Br, I.
In the electrolyte according to the first aspect of the present invention, preferably, R1、R3、R5At least one of them is selected from one of C1-6 alkyl group, C1-6 halogenated alkyl group, C2-6 alkenyl group, C2-6 halogenated alkenyl group, phenyl group, halogenated phenyl group, C1-6 alkoxy group, C1-6 halogenated alkoxy group, phenoxy group and halogenated phenoxy group.
In the electrolyte according to the first aspect of the present invention, preferably, R2、R4、R6Are all selected from fluorine.
In the electrolyte according to the first aspect of the present invention, specifically, the cyclotriphosphazene compound may be selected from one or more of the following compounds;
in the electrolyte according to the first aspect of the present invention, the content of ethylene carbonate may be 0.1% to 3% by mass of the total mass of the electrolyte. When the mass percentage of the ethylene carbonate in the electrolyte is lower than 0.1%, the ethylene carbonate cannot form a complete reticular passive film on the surface of the positive active material, so that the oxidation side reaction of the electrolyte on the surface cannot be effectively prevented; when the mass percentage of the ethylene carbonate in the electrolyte is higher than 3%, an excessively thick passivation film is formed on the surfaces of the anode and the cathode, so that the impedance of the passivation film is high, the transmission of ions in the passivation film is not facilitated, the polarization of the battery is increased, and the performance of the secondary battery is deteriorated.
In the electrolyte according to the first aspect of the present invention, the content of the cyclotriphosphazene compound may be 0.1% to 10% of the total mass of the electrolyte. When the mass percentage of the cyclotriphosphazene compound in the electrolyte is 0.1 percent, the reaction of the cyclotriphosphazene compound on the surface of the negative electrode to generate a solid electrolyte interface film is insufficient, and the improvement effect on the performance of the secondary battery is not obvious; when the mass percentage of the cyclotriphosphazene compound in the electrolyte is higher than 10%, the viscosity of the electrolyte is remarkably increased, and the conductivity of the electrolyte is reduced, so that the migration of ions is slowed down, and the performance of the secondary battery is deteriorated.
In the electrolyte according to the first aspect of the present invention, the organic solvent may be selected from at least two of Ethylene Carbonate (EC), propylene carbonate, butylene carbonate, fluoroethylene carbonate, Ethyl Methyl Carbonate (EMC), dimethyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone, γ -butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, and ethyl butyrate.
In the electrolytic solution according to the first aspect of the invention, the electrolyte salt may be selected from a lithium salt, a sodium salt, or a zinc salt, depending on the secondary battery to which the electrolytic solution is applied.
In the electrolytic solution according to the first aspect of the invention, the concentration of the electrolyte salt is 0.5M to 1.5M. Preferably, the concentration of the electrolyte salt is 0.8M to 1.2M.
In the electrolyte according to the first aspect of the present invention, the additive may further include one or more of Vinylene Carbonate (VC), vinyl sulfate (DTD), 1, 3-propane sultone (1,3-PS), tris (trimethylsilane) phosphate (TMSP), and tris (trimethylsilane) borate (TMSB) to further improve the performance of the secondary battery.
In the electrolyte according to the first aspect of the present invention, the electrolyte may be prepared by a conventional method, for example, by uniformly mixing the materials in the electrolyte.
Next, a secondary battery according to a second aspect of the invention is explained.
A secondary battery according to a second aspect of the invention includes the electrolyte according to the first aspect of the invention.
In the secondary battery according to the second aspect of the invention, the secondary battery further includes a positive electrode tab, a negative electrode tab, and a separator.
In the secondary battery according to the second aspect of the invention, the positive electrode tab may include a positive electrode current collector and a positive electrode slurry layer that is disposed on the positive electrode current collector and contains a positive electrode active material.
In the secondary battery according to the second aspect of the present invention, the negative electrode tab may include a negative electrode current collector and a negative electrode slurry layer disposed on the negative electrode current collector and including a negative electrode active material.
In the secondary battery according to the second aspect of the present invention, the specific kind of the separator is not particularly limited, and may be any separator material used in the prior art, such as polyethylene, polypropylene, polyvinylidene fluoride, and multilayer composite films thereof, but is not limited thereto.
In the secondary battery according to the second aspect of the invention, the secondary battery may be a lithium ion secondary battery, a sodium ion secondary battery, or a zinc ion secondary battery. When the secondary battery is a lithium ion secondary batteryWhen the battery is used, the positive active material can be selected from one or more of lithium cobaltate, lithium iron phosphate, lithium manganate, nickel manganese cobalt ternary material and nickel cobalt aluminum ternary material, the negative active material can be selected from graphite and/or silicon, and the electrolyte salt (namely lithium salt) can be selected from LiPF6、LiClO4、LiAsF6One or more of LiTFSI, LiTFS, LiFSI, LiDFOB and LiBOB.
The present application is further illustrated below with reference to examples. It is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application, which selects a soft pack lithium ion secondary battery for the relevant tests.
The reagents, materials and apparatuses used in the examples and comparative examples were commercially available unless otherwise specified.
The lithium ion secondary batteries of examples 1 to 21 and comparative examples 1 to 6 were each prepared as follows.
(1) Preparation of positive plate
LiNi serving as a positive electrode active material0.8Co0.15Mn0.15O2Mixing a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:1.4:1.6, adding the mixture into a solvent N-methyl pyrrolidone (NMP), and stirring the mixture under the action of a vacuum stirrer until the system becomes uniform and transparent to obtain positive slurry, wherein the solid content in the positive slurry is 77 wt%; and uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil, drying at 85 ℃, then carrying out cold pressing, trimming, cutting into pieces, slitting, and finally drying for 4 hours at 85 ℃ under a vacuum condition to obtain the positive electrode plate.
(2) Preparation of negative plate
Mixing a negative electrode active material graphite, a conductive agent Super P, a thickening agent sodium carboxymethyl cellulose (CMC) and a binder styrene-butadiene rubber emulsion (SBR) according to a mass ratio of 96.4:1.5:0.5:1.6, adding the mixture into solvent deionized water, and obtaining negative electrode slurry under the action of a vacuum stirrer, wherein the solid content in the negative electrode slurry is 54 wt%; and uniformly coating the negative electrode slurry on a copper foil of a negative electrode current collector, drying at 85 ℃, then carrying out cold pressing, trimming, cutting and slitting, and finally drying for 12h at 120 ℃ under a vacuum condition to obtain the negative electrode sheet.
(3) Preparation of electrolyte
At water content<In a 10ppm argon atmosphere glove box, EC, EMC, DEC were mixed in a mass ratio of EC to EMC to DEC of 30:50:20 as an organic solvent, followed by sufficiently dried lithium salt LiPF6Dissolving in mixed organic solvent, adding additive, and mixing to obtain electrolyte. Wherein, LiPF6The concentration of (2) is 1 mol/L. Specific kinds and contents of additives used in the electrolyte are shown in table 1. In table 1, the additive amount is a mass percentage calculated based on the total mass of the electrolyte.
(4) Preparation of the separator
A polyethylene film (PE) having a thickness of 16 μm was used as a separator.
(5) Preparation of lithium ion secondary battery
The positive plate, the isolation film and the negative plate are sequentially stacked, the isolation film is positioned between the positive plate and the negative plate to play a role of isolation, then the positive plate and the negative plate are wound into a square bare cell, tabs are welded, the bare cell is arranged in a packaging foil aluminum plastic film, then after baking and dewatering at 80 ℃, corresponding electrolyte is injected and sealed, and then the finished product of the soft-package lithium ion secondary battery is obtained through the procedures of standing, hot cold pressing, formation (0.02C constant current charging to 3.3V, 0.1C constant current charging to 3.6V), shaping, capacity testing and the like, wherein the thickness of the finished product of the soft-package lithium ion secondary battery is 4.0mm, the width of the finished product of the soft-package lithium ion secondary battery is 60mm, and.
TABLE 1 parameters for examples 1-21 and comparative examples 1-6
Next, a test procedure of the lithium ion secondary battery is explained.
(1) Normal temperature cycle performance test of lithium ion secondary battery
At 25 ℃, the lithium ion secondary battery is charged to 4.2V by a constant current of 1C, further charged to a current of 0.05C by a constant voltage of 4.2V, and then discharged to 2.8V by a constant current of 1C, which is a charge-discharge cycle process, and the discharge capacity of the time is the discharge capacity of the lithium ion secondary battery after the first cycle. The lithium ion secondary battery was subjected to 500 cycles of charge/discharge tests in accordance with the above-described method.
The capacity retention (%) after 500 cycles of the lithium ion secondary battery was the discharge capacity after 500 cycles/the discharge capacity after the first cycle × 100%.
(2) High temperature storage performance test of lithium ion secondary battery
Charging the lithium ion secondary battery at 25 ℃ with a 1C constant current to a voltage of 4.2V, then charging with a 4.2V constant voltage to a current of 0.05C, then discharging with a 1C constant current to a voltage of 2.8V, and testing the discharge capacity of the lithium ion secondary battery at that time, wherein the discharge capacity is marked as C0(ii) a Charging the lithium ion secondary battery with a constant current of 1C to a voltage of 4.2V, then charging with a constant voltage of 4.2V to a current of 0.05C, putting the lithium ion secondary battery into a constant temperature box at 60 ℃, keeping the temperature for 90 days, taking out the lithium ion secondary battery, discharging with a constant current of 1C to a voltage of 2.8V, testing the discharge capacity of the lithium ion secondary battery at the moment, and marking the discharge capacity as C1。
Capacity retention (%) of lithium ion secondary battery after 90 days of storage at 60 ℃ [ (% ]) C1/C0×100％。
(3) High temperature thermal stability test of lithium ion secondary battery
The lithium ion secondary battery subjected to 500 cycles was charged at 25 ℃ at a constant current of 0.5C to a voltage of 4.2V and further charged at a constant voltage of 4.2V to a current of 0.05C, and then the lithium ion secondary battery was placed in a high-temperature furnace at 150 ℃ for 1 hour, and the state of the lithium ion secondary battery was observed.
Table 2 results of the performance test of examples 1 to 21 and comparative examples 1 to 6.
As can be seen from comparative examples 1 to 3, when ethylene carbonate alone (comparative example 2) or cyclotriphosphazene compound alone (comparative example 3) was added to the electrolyte, both the normal temperature cycle performance and the high temperature storage performance of the lithium ion secondary battery were slightly improved as compared with comparative example 1, but the improvement effect was not significant, and the high temperature thermal stability of the lithium ion secondary battery was still poor. In examples 1 to 18, ethylene carbonate and a cyclotriphosphazene compound were simultaneously added to the electrolyte, so that the normal-temperature cycle performance and the high-temperature storage performance of the lithium ion secondary battery were significantly improved, and the thermal stability of the lithium ion secondary battery was also significantly improved. In examples 19 to 21, in which one or more of vinyl sulfate, 1, 3-propanesultone, and tris (trimethylsilane) phosphate were added in addition to the ethylene carbonate and cyclotriphosphazene compound, the normal-temperature cycle performance and the high-temperature storage performance of the lithium ion secondary battery were further improved, and the stability of the lithium ion secondary battery was not deteriorated.
It can be seen from the comparison of examples 1-5 and comparative example 4 that when the content of ethylene carbonate in the electrolyte is too high, the resistance of the passivation film is high due to the formation of an excessively thick passivation film on the surfaces of the positive and negative electrodes, which is not favorable for the transmission of lithium ions in the passivation film, and the normal temperature cycle performance, high temperature storage performance and high temperature thermal stability of the lithium ion secondary battery are not improved but deteriorated.
As can be seen from the comparison of examples 3, 6 to 9 and comparative example 5, when the content of the cyclotriphosphazene compound in the electrolyte is excessively high, the normal temperature cycle performance, the high temperature storage performance and the high temperature thermal stability of the lithium ion secondary battery are not but not improved but deteriorated because it significantly increases the viscosity of the electrolyte, decreases the conductivity of the electrolyte and slows down the migration of lithium ions.
In summary, it is found that when the electrolyte containing cyclotriphosphazene compound and ethylene carbonate is applied to the lithium ion secondary battery, the normal temperature cycle performance and the high temperature storage performance of the lithium ion secondary battery can be improved, and the thermal stability of the lithium ion secondary battery at high temperature can be improved.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. An electrolyte, comprising:
an electrolyte salt;
an organic solvent; and
an additive;
it is characterized in that the preparation method is characterized in that,
the additive comprises a cyclotriphosphazene compound and ethylene carbonate.
2. The electrolyte as claimed in claim 1, wherein the cyclotriphosphazene compound is selected from one or more compounds represented by formula 1;
wherein,
R1、R2、R3、R4、R5、R6each independently selected from one of H, F, Cl, Br, I, C1-20 alkyl, C1-20 halogenated alkyl, C2-20 alkenyl, C2-20 halogenated alkenyl, C6-26 aryl, C6-26 halogenated aryl, C1-20 alkoxy, C1-20 halogenated alkoxy, C6-26 aryloxy and C6-26 halogenated aryloxy;
R1、R3、R5at least one of the above groups is selected from one of C1-20 alkyl group, C1-20 halogenated alkyl group, C2-20 alkenyl group, C2-20 halogenated alkenyl group, C6-26 aryl group, C6-26 halogenated aryl group, C1-20 alkoxy group, C1-20 halogenated alkoxy group, C6-26 aryloxy group and C6-26 halogenated aryloxy group;
R2、R4、R6at least two of (a) are each independently selected from one of F, Cl, Br, I.
3. The electrolyte of claim 2,
R1、R3、R5at least one of the alkyl group and the halogenated alkyl group is selected from one of an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a halogenated alkenyl group having 2 to 6 carbon atoms, a phenyl group, a halogenated phenyl group, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkoxy group having 1 to 6 carbon atoms, a phenoxy group and a halogenated phenoxy group;
R2、R4、R6are all selected from fluorine.
4. The electrolyte of claim 3, wherein the cyclotriphosphazene compound is selected from one or more of the following compounds;
5. the electrolyte of claim 1, wherein the cyclotriphosphazene compound is present in an amount of 0.1% to 10% by weight of the total electrolyte.
6. The electrolyte of claim 1, wherein the ethylene carbonate is present in an amount of 0.1% to 3% by weight of the total electrolyte.
7. The electrolyte of claim 1, wherein the organic solvent is selected from at least two of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, propyl methyl carbonate, propyl ethyl carbonate, 1, 4-butyrolactone, γ -butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, and ethyl butyrate.
8. The electrolyte of claim 1, wherein the concentration of the electrolyte salt in the electrolyte is between 0.5M and 1.5M, preferably between 0.8M and 1.2M.
9. The electrolyte of any one of claims 1-8, wherein the additive further comprises one or more of vinylene carbonate, vinyl sulfate, 1, 3-propane sultone, tris (trimethylsilane) phosphate, tris (trimethylsilane) borate.
10. A secondary battery, characterized by comprising the electrolyte according to any one of claims 1-9.
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| PCT/CN2017/093748 WO2018054153A1 (en) | 2016-09-23 | 2017-07-20 | Electrolyte, and secondary battery |
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| CN110994021A (en) * | 2019-11-19 | 2020-04-10 | 惠州市豪鹏科技有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
| CN114175342A (en) * | 2019-12-24 | 2022-03-11 | 宁德时代新能源科技股份有限公司 | Secondary battery and device containing the same |
| US11961961B2 (en) | 2019-12-24 | 2024-04-16 | Contemporary Amperex Technology Co., Limited | Secondary battery and apparatus containing the same |
| CN114094208A (en) * | 2021-10-13 | 2022-02-25 | 瑞海泊有限公司 | Electrolytes and Aqueous Zinc-Ion Batteries for Aqueous Zinc-Ion Batteries |
| CN115863766A (en) * | 2023-01-18 | 2023-03-28 | 如鲲(江苏)新材料科技有限公司 | Non-aqueous electrolyte and lithium ion battery |
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| WO2018054153A1 (en) | 2018-03-29 |
| CN107871889B (en) | 2020-10-13 |
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