CN112310467A - Lithium ion battery - Google Patents

Lithium ion battery Download PDF

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Publication number
CN112310467A
CN112310467A CN201910700267.4A CN201910700267A CN112310467A CN 112310467 A CN112310467 A CN 112310467A CN 201910700267 A CN201910700267 A CN 201910700267A CN 112310467 A CN112310467 A CN 112310467A
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carbonate
formula
lini
lithium ion
carbon atoms
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Inventor
邓永红
胡时光
万婷
康媛媛
钱韫娴
张�浩
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Shenzhen Capchem Technology Co Ltd
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Shenzhen Capchem Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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

Abstract

The invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a non-aqueous electrolyte and a diaphragm, wherein the positive electrode contains a positive electrode active material, and the positive electrode active material comprises LiNi (represented by formulas 1-4)xCoyMnzL(1‑x‑y‑z)O2、LiCox’L(1‑x’)O2、LiNix”L’y’Mn(2‑x”‑y’)O4And Liz’MPO4At least one of the compounds shown, wherein L, L ', M, x, y, z, x', y ', z' are defined in the specification, the nonaqueous electrolytic solution comprises an organic solvent, a lithium salt, and an additive comprising an unsaturated bisphosphate of formula 5, wherein R is1、R2、R3、R4And R5As defined in the specification. The lithium ion battery provided by the invention can give consideration to both the high-temperature storage performance and the cycle performance of the battery.

Description

Lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery which can give consideration to both the high-temperature storage performance and the cycle performance of the battery.
Background
Lithium ion batteries have been developed in the field of portable electronic products due to their high operating voltage, high safety, long life, no memory effect, and the like. With the development of new energy automobiles, the lithium ion battery has a huge application prospect in a power supply system for the new energy automobiles.
As one of the most important components of a lithium ion battery, an electrolyte plays a crucial role in improving the energy density, the cycle stability, and the like of the lithium ion battery. During the charging and discharging process of the lithium ion battery, the accompanying Li+The reversible intercalation/deintercalation reaction can lead the electrolyte and the electrode material to generate a series of reactions, and a layer of solid electrolyte interface film (SEI film) covering the surface of the electrode material is formed. As an electronic insulator and a lithium ion conductor, the stable SEI film can prevent the electrolyte from further contacting with an electrode material, and has positive effects on the electrochemical performance and safety performance of the lithium ion battery. On the contrary, the unstable SEI film causes the continuous consumption and reaction of lithium ions, and generates a series of irreversible byproducts, which cause the expansion of the battery, increase the internal resistance, even cause fire or explosion, and cause great hidden troubles to the safety of the battery. Therefore, the stability of the SEI film determines the performance of the lithium ion battery.
Many researchers improve the stability of the SEI film of the lithium ion battery and various performances of the battery by selecting different film forming additives (such as vinylene carbonate, fluoroethylene carbonate and ethylene carbonate). Compared with organic solvents and lithium salts, the additive has the advantages of small requirement amount, remarkable effect and low cost. Therefore, the development of additives has become a core technology of electrolyte development. AurThe additive Vinylene Carbonate (VC) is researched by electrochemical methods and spectral methods such as bach and the like, and the VC is found to improve the cycle performance of the battery, particularly the cycle performance of the battery at high temperature and reduce the irreversible capacity. The main reason is that VC can be polymerized on the surface of graphite to generate a polyalkyl lithium carbonate film, thereby inhibiting the reduction of solvent and salt anions. LiClO at 1mol/L of G.H.Wrodnigg et al4Ethylene Sulfite (ES) or Propylene Sulfite (PS) with 5% (volume fraction) is added into Propylene Carbonate (PC), so that PC molecules can be effectively prevented from being embedded into a graphite electrode, and the low-temperature performance of the electrolyte can be improved. The reason for this may be, for example, that the reduction potential of ES is about 2V (vs. Li/Li)+) The SEI film is formed on the surface of the graphite negative electrode in preference to the solvent reduction. Although research shows that functional additives play a very important role in improving the performance of the battery, and the addition of the additives can make up for some defects of the electrolyte, research work on the aspect is not mature so far, for example, few reports on additives for increasing the working temperature range of the lithium ion battery exist, and the types of the additives particularly applied to high temperature are limited.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a lithium ion battery which can give consideration to both the high-temperature storage performance and the cycle performance of the battery.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a lithium ion battery comprising a positive electrode, a negative electrode, a nonaqueous electrolytic solution, and a separator provided between the positive electrode and the negative electrode, the positive electrode containing a positive electrode active material including at least one compound of compounds represented by formula 1, formula 2, formula 3, and formula 4:
LiNixCoyMnzL(1-x-y-z)O2
in the formula 1, the compound is shown in the specification,
LiCox’L(1-x’)O2
in the formula (2), the first and second groups,
LiNix”L’y’Mn(2-x”-y’)O4
in the formula 3, the first step is,
Liz’MPO4
in the formula (4), the first and second groups,
wherein L is at least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, x + z is more than 0 and less than or equal to 1, x 'is more than 0 and less than or equal to 0.3 and less than or equal to 0.6, y' is more than or equal to 0.01 and less than or equal to 0.2, L 'is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, z' is more than or equal to 0.5 and less than or equal to 1, M is at least one of Fe, Mn and Co,
the nonaqueous electrolytic solution contains an organic solvent, a lithium salt and an additive, wherein the additive comprises an unsaturated bisphosphate shown in formula 5:
Figure BDA0002150605660000021
wherein R is1、R2、R3、R4Each independently selected from the group consisting of substituted or unsubstituted alkyl groups of 1 to 5 carbon atoms, substituted or unsubstituted ether groups of 1 to 5 carbon atoms, and substituted or unsubstituted unsaturated hydrocarbon groups of 2 to 5 carbon atoms, provided that R1、R2、R3、R4At least one of which is the substituted or unsubstituted unsaturated hydrocarbon group of 2 to 5 carbon atoms, R5Selected from substituted or unsubstituted alkylene groups of 1 to 5 carbon atoms, and substituted or unsubstituted ether groups of 1 to 5 carbon atoms.
As a preferred embodiment of the present invention, the positive active material includes LiCoO2、LiFePO4、LiNi0.5Mn1.5O4、LiMn2O4、LiFe0.7Mn0.3PO4、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co01Mn0.1O2、LiNi0.8Co0.15Mn0.05O2、LiNi0.85Co0.1Mn0.05O2、LiNi0.88Co0.08Mn0.04O2、LiNi0.88Co0.1Mn0.02O2、Li1.02Ni0.8Co0.15Mn0.05O2、Li1.02Ni0.85Co0.1Mn0.05O2、Li1.02Ni0.88Co0.08Mn0.04O2、LiNi0.8Co0.15Al0.05O2、LiNi0.88Co0.1Al0.02O2、LiNi0.85Co0.1Al0.05O2、LiNi0.88Co0.08Al0.04O2、Li1.02Ni0.88Co0.08Al0.04O2One or more of (a).
As a preferred embodiment of the present invention, the alkyl group of 1 to 5 carbon atoms may be selected from, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl.
As a preferred embodiment of the present invention, the unsaturated hydrocarbon group of 2 to 5 carbon atoms may be selected from, for example, vinyl, propenyl, allyl, butenyl, pentenyl, methylvinyl, methallyl, ethynyl, propynyl, propargyl, butynyl, pentynyl.
As a preferred embodiment of the present invention, the alkylene group having 1 to 5 carbon atoms may be selected from, for example, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, isopentylene, sec-pentylene, and neopentylene.
As a preferred embodiment of the present invention, the ether group having 1 to 5 carbon atoms may be selected from, for example, methyl ether, ethyl ether, methyl ethyl ether, propyl ether, methyl propyl ether, and ethyl propyl ether.
As a preferred embodiment of the present invention, the substitution is a substitution of one or more hydrogen elements with halogen; preferably, the halogen is fluorine, chlorine, bromine and iodine; further preferably, the halogen is fluorine.
As a particularly preferred embodiment of the present invention, the halogen-substituted alkyl group of 1 to 5 carbon atoms is a fluoroalkyl group of 1 to 5 carbon atoms in which one or more hydrogen elements in the alkyl group of 1 to 5 carbon atoms are substituted with fluorine elements.
As a particularly preferred embodiment of the present invention, the halogen-substituted unsaturated hydrocarbon group of 2 to 5 carbon atoms is a fluorinated unsaturated hydrocarbon group of 1 to 5 carbon atoms obtained by substituting one or more hydrogen elements in the unsaturated hydrocarbon group of 2 to 5 carbon atoms with fluorine element.
As a particularly preferred embodiment of the present invention, the halogen-substituted alkylene group of 1 to 5 carbon atoms is a fluoroalkylene group of 1 to 5 carbon atoms in which one or more hydrogen elements in the alkylene group of 1 to 5 carbon atoms are substituted with fluorine elements.
As a particularly preferred embodiment of the present invention, the halogen-substituted ether group of 1 to 5 carbon atoms is a fluoroether group of 1 to 5 carbon atoms obtained by substituting one or more hydrogen elements in an ether group of 1 to 5 carbon atoms with a fluorine element.
As a more specific preferred embodiment of the present invention, the fluoroether group of 1 to 5 carbon atoms may be selected from, for example, fluoromethyl ether, fluoroethyl ether, fluoromethyl ether, fluoropropyl ether, fluoromethyl propyl ether, and fluoroethyl propyl ether.
As still further preferred embodiments of the present invention, the compounds represented by formula 5 are compounds 1 to 22 listed in table 1 below.
Table 1: representative preferred compounds 1 to 22 of the compound represented by formula 5 of the present invention
Figure BDA0002150605660000041
Figure BDA0002150605660000051
In a preferred embodiment of the present invention, the content of the unsaturated bisphosphate represented by the formula 5 is 10ppm or more based on the total mass of the nonaqueous electrolytic solution. In a further preferred embodiment of the present invention, the content of the unsaturated bisphosphate represented by the formula 5 is 5% or less with respect to the total mass of the nonaqueous electrolytic solution. For example, the content of the compound represented by the formula 5 is 10ppm to 5%, 20ppm to 2%, 30ppm to 1%, 50ppm to 0.5%, 100ppm to 0.3%, 200ppm to 0.2%, 300 ppm to 1000ppm, 500ppm to 800ppm, or any value therebetween, with respect to the total mass of the nonaqueous electrolytic solution.
In a preferred embodiment of the present invention, the organic solvent is a mixture of a cyclic carbonate and a chain carbonate.
In a further preferred embodiment of the present invention, the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate, and the chain carbonate is at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propyl methyl carbonate.
In a preferred embodiment of the present invention, the lithium salt is selected from LiPF6、LiBF4、LiPO2F2、LiTFSI、LiBOB、LiDFOB、LiN(SO2F)2At least one of (1).
In a preferred embodiment of the present invention, the additive further comprises at least one of an unsaturated cyclic carbonate, a fluorinated cyclic carbonate, a cyclic sultone, and a cyclic sulfate.
In a further preferred embodiment of the present invention, the unsaturated cyclic carbonate is at least one selected from vinylene carbonate (CAS:872-36-6), vinylene carbonate (CAS:4427-96-7), and methylene vinyl carbonate (CAS:124222-05-5), the fluorinated cyclic carbonate is at least one selected from fluoroethylene carbonate (CAS:114435-02-8), trifluoromethyl vinyl carbonate (CAS:167951-80-6), and difluorovinyl carbonate (CAS:311810-76-1), and the cyclic sultone is at least one selected from 1, 3-propane sultone (CAS:1120-71-4), 1, 4-butane sultone (CAS:1633-83-6), and propenyl-1, 3-sultone (CAS:21806-61-1), the cyclic sulfate is at least one selected from vinyl sulfate (CAS:1072-53-3) and 4-methyl vinyl sulfate (CAS: 5689-83-8).
In a further preferred embodiment of the present invention, the content of the unsaturated cyclic carbonate, the content of the fluorinated cyclic carbonate, the content of the cyclic sultone and the content of the cyclic sulfate are 0.1% to 5%, 0.1% to 30%, 0.1% to 5% and 0.1% to 5%, respectively, based on the total amount of the nonaqueous electrolytic solution.
As a preferable aspect of the present invention, the negative electrode includes a negative electrode active material selected from a metalloid capable of alloying with lithium, a carbonaceous active material, or a combination thereof. As a preferred aspect of the present invention, the metalloid capable of alloying with lithium comprises silicon, a silicon-carbon composite comprising silicon particles, or a combination thereof, and the carbonaceous active material comprises graphite.
Although the mechanism of action of the unsaturated bisphosphate represented by formula 5 in the nonaqueous electrolytic solution in the lithium ion battery of the present invention is not sufficiently clear, the inventors speculate that when the unsaturated bisphosphate represented by formula 5 is present in the electrolytic solution, it contacts the surface of the positive electrode and reacts, and the reaction product can protect the positive electrode and suppress elution of metal ions of the positive electrode. In addition, the unsaturated bisphosphate shown in formula 5 can react with LiF, so that the content of high-impedance component LiF in the passivation film on the surface of the electrode is reduced, lithium ions can pass through the electrode, and the high-temperature storage performance and the cycle performance of the lithium ion battery can be obviously improved.
The content of the compound represented by formula 5 is 10ppm or more relative to the total mass of the nonaqueous electrolytic solution. When the amount is less than 10ppm, it may be difficult to sufficiently form a passivation film on the surfaces of the positive and negative electrodes, and it may be difficult to sufficiently improve the high-temperature storage performance of the nonaqueous electrolyte battery. When the content of the compound represented by formula 5 is too high, for example, more than 5%, an excessively thick passivation film may be formed on the surfaces of the positive and negative electrodes, increasing the internal resistance of the battery, thereby decreasing the cycle performance of the battery and causing an increase in the cost of the electrolyte.
The non-aqueous electrolyte in the lithium ion battery also comprises at least one of unsaturated cyclic carbonate, fluorinated cyclic carbonate, cyclic sultone and cyclic sulfate as a film forming additive, so that a more stable SEI film can be formed on the surface of a graphite negative electrode, and the cycle performance of the lithium ion battery is remarkably improved.
The non-aqueous electrolyte in the lithium ion battery adopts the mixed solution of the cyclic carbonate organic solvent with high dielectric constant and the chain carbonate organic solvent with low viscosity as the solvent of the lithium ion battery electrolyte, so that the mixed solution of the organic solvent has high ionic conductivity, high dielectric constant and low viscosity at the same time.
Detailed Description
The present invention provides a lithium ion battery comprising a positive electrode, a negative electrode, a nonaqueous electrolytic solution, and a separator disposed between the positive electrode and the negative electrode, wherein the positive electrode contains a positive electrode active material including at least one compound selected from compounds represented by formula 1, formula 2, formula 3, and formula 4:
LiNixCoyMnzL(1-x-y-z)O2
in the formula 1, the compound is shown in the specification,
LiCox’L(1-x’)O2
in the formula (2), the first and second groups,
LiNix”L’y’Mn(2-x”-y’)O4
in the formula 3, the first step is,
Liz’MPO4
in the formula (4), the first and second groups,
wherein L is at least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, x + z is more than 0 and less than or equal to 1, x 'is more than 0 and less than or equal to 0.3 and less than or equal to 0.6, y' is more than or equal to 0.01 and less than or equal to 0.2, L 'is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, z' is more than or equal to 0.5 and less than or equal to 1, M is at least one of Fe, Mn and Co,
the nonaqueous electrolytic solution contains an organic solvent, a lithium salt and an additive, wherein the additive comprises an unsaturated bisphosphate shown in formula 5:
Figure BDA0002150605660000071
wherein R is1、R2、R3、R4Each independently selected from the group consisting of substituted or unsubstituted alkyl groups of 1 to 5 carbon atoms, substituted or unsubstituted ether groups of 1 to 5 carbon atoms, and substituted or unsubstituted unsaturated hydrocarbon groups of 2 to 5 carbon atoms, provided that R1、R2、R3、R4At least one of which is the substituted or unsubstituted unsaturated hydrocarbon group of 2 to 5 carbon atoms, R5Selected from substituted or unsubstituted alkylene groups of 1 to 5 carbon atoms, and substituted or unsubstituted ether groups of 1 to 5 carbon atoms.
The positive active material includes LiCoO2、LiFePO4、LiNi0.5Mn1.5O4、LiMn2O4、LiFe0.7Mn0.3PO4、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co01Mn0.1O2、LiNi0.8Co0.15Mn0.05O2、LiNi0.85Co0.1Mn0.05O2、LiNi0.88Co0.08Mn0.04O2、LiNi0.88Co0.1Mn0.02O2、Li1.02Ni0.8Co0.15Mn0.05O2、Li1.02Ni0.85Co0.1Mn0.05O2、Li1.02Ni0.88Co0.08Mn0.04O2、LiNi0.8Co0.15Al0.05O2、LiNi0.88Co0.1Al0.02O2、LiNi0.85Co0.1Al0.05O2、LiNi0.88Co0.08Al0.04O2、Li1.02Ni0.88Co0.08Al0.04O2One or more of (a).
The alkyl group of 1 to 5 carbon atoms may be selected from, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl.
The unsaturated hydrocarbon group of 2 to 5 carbon atoms may be selected from, for example, vinyl, propenyl, allyl, butenyl, pentenyl, methylvinyl, methallyl, ethynyl, propynyl, propargyl, butynyl, pentynyl.
The alkylene group of 1 to 5 carbon atoms may be selected from, for example, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, isopentylene, sec-pentylene, neopentylene.
The ether group of 1 to 5 carbon atoms may be selected from, for example, methyl ether, ethyl ether, methyl ethyl ether, propyl ether, methyl propyl ether, ethyl propyl ether.
The substitution is that one or more hydrogen elements are substituted by halogen; preferably, the halogen is fluorine, chlorine, bromine and iodine; further preferably, the halogen is fluorine.
Specifically, the halogen-substituted alkyl group of 1 to 5 carbon atoms is a fluoroalkyl group of 1 to 5 carbon atoms in which one or more hydrogen elements are substituted with fluorine elements in the alkyl group of 1 to 5 carbon atoms.
Specifically, the halogen-substituted unsaturated hydrocarbon group of 2 to 5 carbon atoms is a fluorinated unsaturated hydrocarbon group of 2 to 5 carbon atoms in which one or more hydrogen elements are substituted with fluorine elements in the unsaturated hydrocarbon group of 2 to 5 carbon atoms.
Specifically, the halogen-substituted alkylene group having 1 to 5 carbon atoms is a fluorinated alkylene group having 1 to 5 carbon atoms in which one or more hydrogen elements are substituted with fluorine elements in the alkylene group having 1 to 5 carbon atoms.
Specifically, the halogen-substituted ether group having 1 to 5 carbon atoms is a fluoroether group having 1 to 5 carbon atoms obtained by substituting one or more hydrogen elements in an ether group having 1 to 5 carbon atoms with a fluorine element.
Further specifically, the fluoroether group of 1 to 5 carbon atoms may be selected from, for example, fluoromethyl ether, fluoroethyl ether, fluoromethyl ethyl ether, fluoropropyl ether, fluoromethyl propyl ether, and fluoroethyl propyl ether.
The method for preparing the compound of formula 5 can be known to those skilled in the art based on the common general knowledge in the field of chemical synthesis, knowing the structural formula of the compound. For example, the compound of formula 5 can be prepared by reacting phosphorus oxychloride with corresponding alcohol in an ether solvent at low temperature (-10 to 0 ℃) and normal pressure by using triethylamine as an acid-binding agent to generate corresponding phosphate, and then performing recrystallization or column chromatography purification. Taking compounds 1, 6 and 15 as examples, the synthetic route is illustrated below:
Figure BDA0002150605660000081
Figure BDA0002150605660000091
the present invention is further illustrated by way of the following non-limiting examples and comparative examples. I. Examples 1 to 11 and comparative examples 1 to 5
1) Preparation of the electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) were mixed in a mass ratio of EC: DEC: EMC ═ 1:1:1, and then lithium hexafluorophosphate (LiPF) was added6) To a molar concentration of 1mol/L, a base electrolyte was prepared. Then, as shown in Table 2, a specified amount of the compound represented by formula 5 and/or a specified amount of other compound shown in Table 1 was added or not added.
Specifically, based on the total mass of the base electrolyte, 50ppm of compound 1, 500ppm of compound 1, 1000ppm of compound 1, 500ppm of compound 2, 500ppm of compound 3, 500ppm of compound 4, 500ppm of compound 6 were added to examples 1 to 7, respectively; examples 8-11 were charged with 500ppm of Compound 1 and 1% Vinylene Carbonate (VC), 500ppm of Compound 1 and 1% fluoroethylene carbonate (FEC), 500ppm of Compound 1 and 1% 1, 3-Propanesultone (PS), 500ppm of Compound 1 and 1% ethylene sulfate (DTD), respectively; comparative example 1 the compound represented by formula 5 and other compounds were not added; comparative examples 2 to 5 the compound represented by formula 5 was not added, but 1% of VC, 1% of FEC, 1% of PS, and 1% of DTD were added, respectively.
2) Preparation of Positive plate
Mixing a positive active material lithium nickel cobalt manganese oxide 4.2VLiNi according to a mass ratio of 93:4:30.5Co0.2Mn0.3O2Conductive carbon black Super-P and a binder polyvinylidene fluoride (PVDF), and then dispersing the mixture in N-methyl-2-pyrrolidone (NMP) to obtain N-butylAnd (3) polar slurry. And uniformly coating the slurry on two sides of the aluminum foil, drying, rolling and vacuum drying, and welding an aluminum outgoing line by using an ultrasonic welding machine to obtain the positive plate, wherein the thickness of the positive plate is 120-.
3) Preparation of negative plate
Mixing artificial graphite serving as a negative electrode active material, conductive carbon black Super-P, Styrene Butadiene Rubber (SBR) serving as a binder and carboxymethyl cellulose (CMC) according to a mass ratio of 94:1:2.5:2.5, and dispersing the mixture in deionized water to obtain negative electrode slurry. Coating the slurry on two sides of the copper foil, drying, rolling and vacuum drying, and welding a nickel outgoing line by using an ultrasonic welding machine to obtain a negative plate, wherein the thickness of the negative plate is 120-150 mu m.
4) Preparation of cell
And placing three layers of diaphragms with the thickness of 20 mu m between the positive plate and the negative plate, then winding the sandwich structure consisting of the positive plate, the negative plate and the diaphragms, flattening the wound body, then placing the flattened wound body into an aluminum foil packaging bag, and baking the flattened wound body in vacuum at 75 ℃ for 48 hours to obtain the battery cell to be injected with liquid.
5) Liquid injection and formation of battery core
And (3) in a glove box with the dew point controlled below-40 ℃, injecting the prepared electrolyte into a battery cell, carrying out vacuum packaging to prepare a lithium ion battery, and standing for 24 hours.
Then the first charge is normalized according to the following steps: charging at 0.05C for 180min, charging at 0.2C to 3.95V, vacuum sealing for the second time, further charging at 0.2C to 4.2V, standing at room temperature for 24h, and discharging at 0.2C to 3.0V.
Examples 12 to 15 and comparative example 6
Base electrolytes were prepared by referring to the methods described in "i. examples 1 to 11 and comparative examples 1 to 5" above, and then, as shown in table 3, a compound represented by formula 5 listed in table 1 and/or other compounds in the specified amounts were added or not added. Specifically, based on the total mass of the electrolyte, 500ppm of compound 1, 50ppm of compound 2, 500ppm of compound 6, 500ppm of compound 8 were added to examples 12 to 15, respectively; comparative example 6 the compound represented by formula 5 was not added andother compounds; in addition, 4.4V LiNi was used as the positive electrode active material in each of examples 12 to 15 and comparative example 60.5Co0.2Mn0.3O2And preparing the positive plate. Negative plates, cells, and liquid injection and formation (charging to 4.4V) of the cells were prepared in the manner described in "i. examples 1 to 11 and comparative examples 1 to 5" above.
Examples 16 to 19 and comparative example 7
Base electrolytes were prepared by referring to the methods described in "i. examples 1 to 11 and comparative examples 1 to 5" above, and then, as shown in table 4, a compound represented by formula 5 listed in table 1 and/or other compounds in the specified amounts were added or not added. Specifically, 500ppm of compound 1, 1000ppm of compound 3, 500ppm of compound 4, 500ppm of compound 9 were added to examples 16 to 19, respectively, based on the total mass of the electrolyte; comparative example 7 the compound represented by formula 5 and other compounds were not added; in addition, LiNi was used as the positive electrode active material in each of examples 16 to 19 and comparative example 70.8Co0.1Mn0.1O2And preparing the positive plate. Negative plates and cells were prepared by the methods described in "i. examples 1 to 11 and comparative examples 1 to 5" above, and injection and formation of cells were performed.
IV, examples 20 to 24 and comparative example 8
Base electrolytes were prepared by referring to the methods described in the above "i. examples 1 to 11 and comparative examples 1 to 5", and then, as shown in table 5, a compound represented by formula 5 listed in table 1 and/or other compounds in the specified amounts were added or not added in the specified amounts. Specifically, 500ppm of compound 1, 50ppm of compound 4, 500ppm of compound 5, 1000ppm of compound 8, 1% of compound 9 were added to examples 20 to 24, respectively, based on the total mass of the electrolyte; comparative example 8 the compound represented by formula 5 and other compounds were not added; in addition, LiCoO was used as the positive electrode active material in each of examples 20 to 24 and comparative example 82And preparing the positive plate. Negative plates, cells, and liquid injection and formation (charging to 4.4V) of the cells were prepared in the manner described in "i. examples 1 to 11 and comparative examples 1 to 5" above.
V. examples 25 to 29 and comparative example 9
With reference to the above "IBase electrolytes were prepared as described in examples 1 to 11 and comparative examples 1 to 5 ", and then, as shown in Table 6, a compound represented by formula 5 shown in Table 1 in the specified amount and/or other compounds in the specified amounts were added or not added. Specifically, 500ppm of compound 1, 50ppm of compound 3, 500ppm of compound 4, 1000ppm of compound 7, 1% of compound 9 were added to examples 25 to 29, respectively, based on the total mass of the electrolyte; comparative example 9 the compound represented by formula 5 and other compounds were not added; in addition, LiFePO was used as the positive electrode active material in each of examples 25 to 29 and comparative example 94And preparing the positive plate. Negative plates, cells, and liquid injection and formation (charging to 3.6V) of the cells were prepared in the manner described in "i. examples 1 to 11 and comparative examples 1 to 5" above.
VI, examples 30-33 and comparative example 10
Base electrolytes were prepared by referring to the methods described in the above "i. examples 1 to 11 and comparative examples 1 to 5", and then, as shown in table 7, a compound represented by formula 5 listed in table 1 and/or other compounds in the specified amounts were added or not added. Specifically, 500ppm of compound 2, 50ppm of compound 3, 500ppm of compound 4, 1000ppm of compound 5 were added to examples 30 to 33, respectively, based on the total mass of the electrolyte; comparative example 10 the compound represented by formula 5 and other compounds were not added; in addition, LiMn was used as the positive electrode active material in each of examples 30 to 33 and comparative example 102O4And preparing the positive plate. Negative plates and cells were prepared by the methods described in "i. examples 1 to 11 and comparative examples 1 to 5" above, and injection and formation of cells were performed.
Performance testing of lithium ion batteries fabricated in examples and comparative examples
In order to verify the performance of the lithium ion batteries of the present invention, the following performance tests were performed on the lithium ion batteries fabricated in the above examples 1 to 33 and comparative examples 1 to 10. The tested performance comprises a high-temperature cycle performance test, a high-temperature storage performance test and a low-temperature performance test, and the specific test method comprises the following steps:
1. high temperature cycle performance test
The lithium ion batteries manufactured in examples 1 to 33 and comparative examples 1 to 10 were placed in an oven at a constant temperature of 45 ℃And is charged to 4.4V (LiNi) with a current of 1C in a constant current manner0.5Co0.2Mn0.3O2Artificial graphite Battery, LiCoO2Artificial graphite battery) or 4.2V (LiNi)0.5Co0.2Mn0.3O2Artificial graphite Battery, LiNi0.8Co0.1Mn0.1O2Artificial graphite Battery, LiMn2O2Artificial graphite battery) or 3.6V (LiFePO)4Artificial graphite cell), constant voltage charging until the current drops to 0.02C, and constant current discharging at 1C to 3.0V or 2.5V (LiFePO)4Artificial graphite cell), cycled as such, and the 1 st discharge capacity and the last discharge capacity were recorded.
The capacity retention for the high temperature cycle was calculated as follows:
battery capacity retention (%) — last discharge capacity/1 st discharge capacity × 100%.
2. High temperature storage Performance test
The lithium ion batteries fabricated in examples 1 to 33 and comparative examples 1 to 10 were formed and then charged to 4.4V (LiNi) at room temperature with a constant current and a constant voltage of 1C0.5Co0.2Mn0.3O2Artificial graphite Battery, LiCoO2Artificial graphite battery) or 4.2V (LiNi)0.5Co0.2Mn0.3O2Artificial graphite Battery, LiNi0.8Co0.1Mn0.1O2Artificial graphite Battery, LiMn2O2Artificial graphite battery), 3.6V (LiFePO)4Artificial graphite battery) was measured for the initial discharge capacity and initial battery thickness, and then discharged to 3V at 1C after storage for 30 days in an environment of 60C, and the retention capacity and recovery capacity of the battery and the battery thickness after storage were measured. The calculation formula is as follows:
battery capacity retention (%) — retention capacity/initial capacity × 100%;
battery capacity recovery (%) — recovery capacity/initial capacity × 100%;
thickness expansion (%) (battery thickness after storage-initial battery thickness)/initial battery thickness × 100%.
Table 2: positive electrode active ingredient, electrolyte composition and battery performance of lithium ion batteries of examples 1 to 11 and comparative examples 1 to 5
Figure BDA0002150605660000131
As can be seen from the data in Table 2, 4.2V LiNi was used0.5Co0.2Mn0.3O2In the case of examples 1 to 7, the high-temperature cycle performance and the high-temperature storage performance of the lithium ion battery were significantly improved compared to those of comparative example 1 due to the addition of the representative compound represented by formula 5 in an amount of 50 to 1000ppm based on the total mass of the nonaqueous electrolyte solution of the lithium ion battery. In examples 8 to 11, compared with comparative examples 2 to 5, the nonaqueous electrolyte solution of the lithium ion battery contains 500ppm of the compound 1 in addition to other compounds, and the high-temperature cycle performance and the high-temperature storage performance of the corresponding lithium ion battery are also obviously improved.
Table 3: positive electrode active ingredient, electrolyte composition and cell performance of lithium ion batteries of examples 12 to 15 and comparative example 6
Figure BDA0002150605660000141
As can be seen from the data in Table 3, 4.4V LiNi was used0.5Co0.2Mn0.3O2In the case of examples 12 to 15, the high-temperature cycle performance and the high-temperature storage performance of the lithium ion battery were significantly improved compared to those of comparative example 6 due to the addition of the representative compound represented by formula 5 in an amount of 50 to 500ppm based on the total mass of the nonaqueous electrolyte solution of the lithium ion battery.
Table 4: positive electrode active ingredient, electrolyte composition and cell performance of lithium ion batteries of examples 16 to 19 and comparative example 7
Figure BDA0002150605660000142
As can be seen from the data in Table 4, LiNi was used0.8Co0.1Mn0.1O2In the case of examples 16 to 19 as the positive electrode active component, the high-temperature cycle performance and the high-temperature storage performance of the corresponding lithium ion batteries were significantly improved as compared with comparative example 7 due to the addition of the representative compound represented by formula 5 in an amount of 500-1000ppm based on the total mass of the nonaqueous electrolyte solution of the lithium ion battery.
Table 5: positive electrode active ingredient, electrolyte composition and cell performance of lithium ion batteries of examples 20 to 24 and comparative example 8
Figure BDA0002150605660000151
As can be seen from the data in Table 5, LiCoO was used2In the case of examples 20 to 24, the high-temperature cycle performance and the high-temperature storage performance of the lithium ion battery were significantly improved compared to those of comparative example 8 due to the addition of the representative compound represented by formula 5 in an amount of 50ppm to 1% based on the total mass of the nonaqueous electrolyte solution of the lithium ion battery.
Table 6: positive electrode active ingredient, electrolyte composition and cell performance of lithium ion batteries of examples 25 to 29 and comparative example 9
Figure BDA0002150605660000152
As can be seen from the data in Table 6, LiFePO was used4In the case of examples 25 to 29, the high-temperature cycle performance and the high-temperature storage performance of the lithium ion batteries were significantly improved compared to those of comparative example 9 due to the addition of the representative compound represented by formula 5 in an amount of 50ppm to 1% based on the total mass of the nonaqueous electrolyte solution of the lithium ion batteries.
Table 7: positive electrode active ingredient, electrolyte composition and battery performance of lithium ion batteries of examples 30 to 33 and comparative example 10
Figure BDA0002150605660000161
As can be seen from the data in Table 7, the use of LiMn is preferred2O4In the case of examples 30 to 33, the high-temperature cycle performance and the high-temperature storage performance of the lithium ion batteries were significantly improved compared to comparative example 10 due to the addition of the representative compound represented by formula 5 in an amount of 50 to 1000ppm based on the total mass of the nonaqueous electrolyte solution of the lithium ion batteries.
3. Low temperature Performance test
The lithium ion batteries of comparative examples 11-16 were made as follows:
comparative example 11 as the positive electrode active ingredients of examples 2 and 4, the compound represented by formula 5 was not added to the base electrolyte but 500ppm of 2-alkynyl-1, 4-bis (di (2-propynyl)) phosphate (ABPP);
comparative example 12 in the same manner as the positive electrode active ingredients of examples 13 and 15, the compound represented by formula 5 was not added to the base electrolyte, but 2-alkynyl-1, 4-bis (di (2-propynyl)) phosphate was added in an amount of 500 ppm;
comparative example 13 in the same manner as the positive electrode active ingredients of example 16 and example 17, the compound represented by formula 5 was not added to the base electrolyte, but 1000ppm of 2-alkynyl-1, 4-bis (di (2-propynyl)) phosphate was added;
comparative example 14 as the positive electrode active materials of examples 21 and 22, 50ppm of 2-alkynyl-1, 4-bis (di (2-propynyl)) phosphate was added in the base electrolyte without adding the compound represented by formula 5;
comparative example 15 in the same manner as the positive electrode active ingredients of examples 25 and 27, the compound represented by formula 5 was not added to the base electrolyte, but 500ppm of 2-alkynyl-1, 4-bis (di (2-propynyl)) phosphate was added;
comparative example 16 in the same manner as the positive electrode active materials of examples 32 and 33, the compound represented by formula 5 was not added to the base electrolyte, but 1000ppm of 2-alkynyl-1, 4-bis (di (2-propynyl)) phosphate was added.
Will carry outThe lithium ion batteries fabricated in examples 2, 4, 13, 15, 16, 17, 21, 22, 25, 27, 32, 33 and comparative examples 11 to 16 were charged to 4.4V (LiNi) with a constant current and a constant voltage of 1C at room temperature after formation0.5Co0.2Mn0.3O2Artificial graphite Battery, LiCoO2Artificial graphite battery), 4.2V (LiNi)0.5Co0.2Mn0.3O2Artificial graphite Battery, LiNi0.8Co0.1Mn0.1O2Artificial graphite Battery, LiMn2O2Artificial graphite battery) or 3.6V (LiFePO)4Artificial graphite battery). The cells were then discharged to 3.0V at a constant current of 1C and the discharge capacity was recorded. Constant current and constant voltage charging to 4.4V (LiNi) at 1C0.5Co0.2Mn0.3O2Artificial graphite Battery, LiCoO2Artificial graphite battery), 4.2V (LiNi)0.5Co0.2Mn0.3O2Artificial graphite Battery, LiNi0.8Co0.1Mn0.1O2Artificial graphite Battery, LiMn2O2Artificial graphite battery) or 3.6V (LiFePO)4Artificial graphite battery), after placing in-20 ℃ environment for 12h, discharging at constant current of 0.2C to 3.0V, recording discharge capacity, and calculating low-temperature discharge efficiency value at-20 ℃ according to the following formula:
a low-temperature discharge efficiency value of-20 ℃ was 0.2C discharge capacity (-20 ℃) per 1C discharge capacity (25 ℃) x 100%.
The lithium ion batteries manufactured in examples 2, 4, 13, 15, 16, 17, 21, 22, 25, 27, 32, 33 and comparative examples 11 to 16 were charged with a 1C constant current and voltage to an SOC of 50% at normal temperature after formation, and were left to stand in an environment at 0 ℃ for 12 hours, and then charged with 0.1C and 0.5C for 10 seconds, left to stand for 40 seconds, and discharged for 10 seconds, and the 0.1C discharge end voltage and the 0.5C discharge end voltage were recorded, and the low temperature resistance (DCIR) at 0 ℃ was calculated according to the following equation:
low temperature at 0 ℃ (0.5C end of discharge-0.1C end of discharge)/(0.5-0.1) × C
Table 8: positive electrode active ingredient, electrolyte composition and low temperature performance of lithium ion batteries of examples 2, 4, 13, 15, 16, 17, 21, 22, 25, 27, 32, 33 and comparative examples 11 to 16
Figure BDA0002150605660000171
Figure BDA0002150605660000181
The examples shown in Table 8 added a representative compound represented by formula 5 in an amount of 50 to 1000ppm relative to the total mass of the nonaqueous electrolyte for a lithium ion battery, while 2-alkynyl-1, 4-bis (di (2-propynyl)) phosphate in an amount of 500-1000ppm relative to the total mass of the nonaqueous electrolyte for a lithium ion battery was added in the corresponding proportion for the same positive electrode material. As can be seen from the data of Table 8, the related examples showed an increase in the value of the low-temperature discharge efficiency at-20 ℃ and a decrease in the value of the low-temperature DCIR at 0 ℃ as compared with the corresponding comparative examples, indicating that both the low-temperature discharge performance and the low-temperature resistance were significantly improved.
The present invention has been described above using specific examples, which are only for the purpose of facilitating understanding of the present invention, and are not intended to limit the present invention. Numerous simple deductions, modifications or substitutions may be made by those skilled in the art in light of the teachings of the present invention. Such deductions, modifications or alternatives also fall within the scope of the claims of the present invention.

Claims (10)

1. A lithium ion battery comprising a positive electrode, a negative electrode, a nonaqueous electrolytic solution, and a separator provided between the positive electrode and the negative electrode, characterized in that the positive electrode contains a positive electrode active material including at least one compound of compounds represented by formula 1, formula 2, formula 3, and formula 4:
LiNixCoyMnzL(1-x-y-z)O2
in the formula 1, the compound is shown in the specification,
LiCox’L(1-x’)O2
in the formula (2), the first and second groups,
LiNix”L’y’Mn(2-x”-y’)O4
in the formula 3, the first step is,
Liz’MPO4
in the formula (4), the first and second groups,
wherein L is at least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, x + z is more than 0 and less than or equal to 1, x 'is more than 0 and less than or equal to 0.3 and less than or equal to 0.6, y' is more than or equal to 0.01 and less than or equal to 0.2, L 'is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, z' is more than or equal to 0.5 and less than or equal to 1, M is at least one of Fe, Mn and Co,
the nonaqueous electrolytic solution contains an organic solvent, a lithium salt and an additive, wherein the additive comprises an unsaturated bisphosphate shown in formula 5:
Figure FDA0002150605650000011
wherein R is1、R2、R3、R4Each independently selected from the group consisting of substituted or unsubstituted alkyl groups of 1 to 5 carbon atoms, substituted or unsubstituted ether groups of 1 to 5 carbon atoms, and substituted or unsubstituted unsaturated hydrocarbon groups of 2 to 5 carbon atoms, provided that R1、R2、R3、R4At least one of which is said substituted or unsubstituted unsaturated hydrocarbon group of 2 to 5 carbon atoms, R5Selected from substituted or unsubstituted alkylene groups of 1 to 5 carbon atoms, and substituted or unsubstituted ether groups of 1 to 5 carbon atoms.
2. The lithium ion battery of claim 1, wherein the positive electrode active material comprises LiCoO2、LiFePO4、LiMn2O4、LiFe0.7Mn0.3PO4、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co01Mn0.1O2、LiNi0.8Co0.15Mn0.05O2、LiNi0.85Co0.1Mn0.05O2、LiNi0.88Co0.08Mn0.04O2、LiNi0.88Co0.1Mn0.02O2、Li1.02Ni0.8Co0.15Mn0.05O2、Li1.02Ni0.85Co0.1Mn0.05O2、Li1.02Ni0.88Co0.08Mn0.04O2、LiNi0.8Co0.15Al0.05O2、LiNi0.88Co0.1Al0.02O2、LiNi0.85Co0.1Al0.05O2、LiNi0.88Co0.08Al0.04O2、Li1.02Ni0.88Co0.08Al0.04O2One or more of (a).
3. The lithium ion battery according to claim 1, wherein in the unsaturated bisphosphate of formula 5,
the alkyl group of 1 to 5 carbon atoms is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl;
the unsaturated alkyl group with 2-5 carbon atoms is selected from vinyl, propenyl, allyl, butenyl, pentenyl, methylvinyl, methallyl, ethynyl, propynyl, propargyl, butynyl and pentynyl;
the alkylene group of 1 to 5 carbon atoms is selected from the group consisting of methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, isopentylene, sec-pentylene, neopentylene;
the ether group with 1-5 carbon atoms is selected from methyl ether, ethyl ether, methyl ethyl ether, propyl ether, methyl propyl ether and ethyl propyl ether;
the substitution is that one or more hydrogen elements are substituted by halogen; preferably, the halogen is fluorine.
4. The lithium ion battery according to claim 3, wherein the unsaturated bisphosphate represented by formula 5 is a compound 1 to 22 below:
Figure FDA0002150605650000021
Figure FDA0002150605650000031
5. the lithium ion battery according to any one of claims 1 to 4, wherein the content of the unsaturated bisphosphate represented by formula 5 is 10ppm or more with respect to the total mass of the nonaqueous electrolytic solution.
6. The lithium ion battery according to claim 5, wherein the content of the unsaturated bisphosphate represented by formula 5 is 5% or less with respect to the total mass of the nonaqueous electrolytic solution.
7. The lithium ion battery according to claim 1, wherein the organic solvent is a mixture of cyclic carbonate and chain carbonate; preferably, the cyclic carbonate is selected from at least one of ethylene carbonate, propylene carbonate and butylene carbonate, and the chain carbonate is selected from at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propyl methyl carbonate.
8. The lithium ion battery of claim 1, wherein the lithium salt is selected from LiPF6、LiBF4、LiPO2F2、LiTFSI、LiBOB、LiDFOB、LiN(SO2F)2At least one of (1).
9. The lithium ion battery of claim 1, wherein the additive further comprises at least one of an unsaturated cyclic carbonate, a fluorinated cyclic carbonate, a cyclic sultone, a cyclic sulfate; preferably, the unsaturated cyclic carbonate is selected from at least one of vinylene carbonate (CAS:872-36-6), ethylene carbonate (CAS:4427-96-7), and methylene ethylene carbonate (CAS:124222-05-5), the fluorinated cyclic carbonate is selected from at least one of fluoroethylene carbonate (CAS:114435-02-8), trifluoromethyl ethylene carbonate (CAS:167951-80-6), and difluoroethylene carbonate (CAS:311810-76-1), and the cyclic sultone is selected from at least one of 1, 3-propane sultone (CAS:1120-71-4), 1, 4-butane sultone (CAS:1633-83-6), and propenyl-1, 3-sultone (CAS:21806-61-1), the cyclic sulfate is at least one selected from vinyl sulfate (CAS:1072-53-3) and 4-methyl vinyl sulfate (CAS: 5689-83-8).
10. The lithium ion battery according to claim 9, wherein the content of the unsaturated cyclic carbonate is 0.1% to 5%, the content of the fluorinated cyclic carbonate is 0.1% to 30%, the content of the cyclic sultone is 0.1% to 5%, and the content of the cyclic sulfate ester is 0.1% to 5%, based on the total amount of the nonaqueous electrolyte.
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