CN110931856B - lithium battery - Google Patents

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CN110931856B
CN110931856B CN201910360569.1A CN201910360569A CN110931856B CN 110931856 B CN110931856 B CN 110931856B CN 201910360569 A CN201910360569 A CN 201910360569A CN 110931856 B CN110931856 B CN 110931856B
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halogen substituted
lithium battery
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electrolyte solution
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CN110931856A (en
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郑明焕
金暻洙
金允熙
金载弘
罗哈娜
柳洙烈
孙美暎
禹明希
李承泰
李河林
车始英
崔善珠
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Samsung SDI Co Ltd
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    • 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
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    • C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D497/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D497/10—Spiro-condensed systems
    • H—ELECTRICITY
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    • 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
    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The lithium battery includes: a cathode comprising a cathode active material, an anode comprising an anode active material, and an organic electrolyte solution between the cathode and the anode, wherein the cathode comprises a carbonaceous nanostructure, and the organic electrolyte solution comprises a first lithium salt, an organic solvent, and a bicyclic sulfate-based compound represented by the following formula 1:<1 (1)>Wherein in formula 1, A 1 、A 2 、A 3 And A 4 Each independently is a covalent bond, substituted or unsubstituted C 1 ‑C 5 Alkylene, carbonyl or sulfinyl, wherein A 1 And A 2 Not all are covalent bonds, and A 3 And A 4 Not all covalent bonds.

Description

Lithium battery
Cross Reference to Related Applications
The present application claims the benefit of U.S. patent application Ser. No. 15/422,873 entitled "lithium Battery" filed on even date 19 at 9 in 2018, and continuing application Ser. No. 16/135,420, the entire contents of which are incorporated herein by reference.
Technical Field
One or more embodiments of the present application relate to a lithium battery.
Background
Lithium batteries are used as driving power sources for portable electronic devices including video cameras, mobile phones, notebook computers, and the like. The lithium secondary battery can be recharged at a high rate and has an energy density per unit weight at least three times that of the existing lead storage battery, nickel-cadmium battery, nickel-hydrogen battery or nickel-zinc battery.
Disclosure of Invention
Various embodiments of the present invention relate to a lithium battery including: a cathode comprising a cathode active material, an anode comprising an anode active material, and an organic electrolyte solution between the cathode and the anode. The cathode includes carbonaceous nanostructures. The organic electrolyte solution includes a first lithium salt, an organic solvent, and a bicyclic sulfate-based compound represented by the following formula 1:
< 1>
Wherein in formula 1, A 1 、A 2 、A 3 And A 4 Each independently is a covalent bond, substituted or unsubstituted C 1 -C 5 Alkylene, carbonyl or sulfinyl, wherein A 1 And A 2 Not all are covalent bonds, and A 3 And A 4 Not all covalent bonds。
A 1 、A 2 、A 3 And A 4 At least one of which is unsubstituted or substituted C 1 -C 5 Alkylene group, wherein substituted C 1 -C 5 The substituent of the alkylene group is at least one selected from the following: halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen-substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl or a polar functional group having at least one heteroatom.
A 1 、A 2 、A 3 And A 4 At least one of which is unsubstituted or substituted C 1 -C 5 Alkylene group, wherein substituted C 1 -C 5 The substituent of the alkylene group is halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
The substituents of the substituted C1-C5 alkylene groups may include polar functional groups having at least one heteroatom. The polar functional group may be at least one selected from the group consisting of: -F, -Cl, -Br, -I, -C (=o) OR 16 、-OR 16 、-OC(＝O)OR 16 、-R 15 OC(＝O)OR 16 、-C(＝O)R 16 、-R 15 C(＝O)R 16 、-OC(＝O)R 16 、-R 15 OC(＝O)R 16 、-C(＝O)-O-C(＝O)R 16 、-R 15 C(＝O)-O-C(＝O)R 16 、-SR 16 、-R 15 SR 16 、-SSR 16 、-R 15 SSR 16 、-S(＝O)R 16 、-R 15 S(＝O)R 16 、-R 15 C(＝S)R 16 、-R 15 C(＝S)SR 16 、-R 15 SO 3 R 16 、-SO 3 R 16 、-NNC(＝S)R 16 、-R 15 NNC(＝S)R 16 、-R 15 N＝C＝S、-NCO、-R 15 -NCO、-NO 2 、-R 15 NO 2 、-R 15 SO 2 R 16 、-SO 2 R 16 、
In the above formula, R 11 And R is 15 May each independently be halogen substituted or unsubstituted C 1 -C 20 Alkylene, halogen substituted or unsubstituted C 2 -C 20 Alkenylene, halogen substituted or unsubstituted C 2 -C 20 Alkynylene, halogen substituted or unsubstituted C 3 -C 12 Cycloalkylene, halogen substituted or unsubstituted C 6 -C 40 Arylene, halogen substituted or unsubstituted C 2 -C 40 Heteroarylene, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl or halogen substituted or unsubstituted C 7 -C 15 Aralkylene radicals. R is R 12 、R 13 、R 14 And R is 16 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 12 Cycloalkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl, halogen substituted or unsubstituted C 7 -C 15 Trialkylsilyl or halogen substituted or unsubstituted C 7 -C 15 Aralkyl group, andrepresenting the binding site to an adjacent atom.
The bicyclic sulfate based compound may be represented by formula 2 or 3:
wherein in formulas 2 and 3, B 1 、B 2 、B 3 、B 4 、D 1 And D 2 Can each independently be-C (E 1 )(E 2 ) -carbonyl or sulfinyl; and E is 1 And E is 2 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
E 1 And E is 2 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 10 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
E 1 And E is 2 Each independently may be at least one selected from the group consisting of hydrogen, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), methyl, ethyl, propyl, isopropyl, butyl, t-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl, and pyridyl.
The bicyclic sulfate based compound may be represented by formula 4 or formula 5:
wherein the method comprises the steps ofIn formula 4 and formula 5, R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 And each independently may be hydrogen, F, cl, br, I, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl, or pyridyl.
The bicyclic sulfate-based compound may be represented by one of the following formulas 6 to 17:
the amount of the compound based on the bicyclic sulfate may be about 0.4wt% to about 4wt% based on the total weight of the organic electrolyte solution.
The amount of the compound based on the bicyclic sulfate may be about 0.4wt% to about 3wt% based on the total weight of the organic electrolyte solution.
The first lithium salt in the organic electrolyte solution may include at least one selected from the group consisting of: liPF (LiPF) 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiClO 4 、LiCF 3 SO 3 、Li(CF 3 SO 2 ) 2 N、LiC 4 F 9 SO 3 、LiAlO 2 、LiAlCl 4 、LiN(C x F 2x+1 SO 2 )(C y F 2y+ 1 SO 2 ) (wherein x is more than or equal to 2 and less than or equal to 20, and y is more than or equal to 2 and less than or equal to 20), liCl and LiI.
Organic compoundThe electrolyte solution may further comprise a cyclic carbonate compound, wherein the cyclic carbonate compound is selected from the group consisting of: vinylene Carbonate (VC); is selected from halogen, cyano (-CN) and nitro (-NO) 2 ) VC substituted by at least one substituent of (a); vinyl Ethylene Carbonate (VEC); selected from halogen, -CN and-NO 2 VEC substituted by at least one substituent of (C); fluoroethylene carbonate (FEC); is selected from halogen, -CN and-NO 2 FEC substituted by at least one substituent of (a).
The amount of the cyclic carbonate compound may be about 0.01wt% to about 5wt% based on the total weight of the organic electrolyte solution.
The organic electrolyte solution may further include a second lithium salt represented by one of the following formulas 18 to 25:
the amount of the second lithium salt may be about 0.1wt% to about 5wt% based on the total weight of the organic electrolyte solution.
The carbonaceous nanostructure may include at least one selected from a one-dimensional carbonaceous nanostructure and a two-dimensional carbonaceous nanostructure.
The carbonaceous nanostructure may include at least one selected from the group consisting of Carbon Nanotubes (CNTs), carbon nanofibers, graphene nanoplatelets, hollow carbon, porous carbon, and mesoporous carbon.
The carbonaceous nanostructures may have an average length of about 1 μm to about 200 μm.
The amount of carbonaceous nanostructures can be from about 0.5wt% to about 5wt%, based on the total weight of the cathode mixture.
The amount of carbonaceous nanostructures can be about 0.5wt% to about 3wt%, based on the total weight of the cathode mixture.
The cathode may include a nickel-containing layered lithium transition metal oxide.
The nickel content in the lithium transition metal oxide may be about 60mol% or more relative to the total moles of transition metal.
Lithium batteries may have a high voltage of about 3.8V or higher.
Drawings
Various features will become apparent to those of ordinary skill in the art from the detailed description of the exemplary embodiments with reference to the accompanying drawings, in which:
fig. 1 shows graphs showing discharge capacities at room temperature of lithium batteries manufactured according to examples 1-1 and 2-1 and comparative example 1-1;
fig. 2 shows graphs showing capacity retention rates at room temperature of lithium batteries of examples 1-1 and 2-1 and comparative example 1-1;
fig. 3 shows graphs showing discharge capacities of lithium batteries of examples 1-1 and 2-1 and comparative example 1-1 at high temperatures;
fig. 4 shows graphs showing capacity retention rates at high temperatures of the lithium batteries of examples 1-1 and 2-15 and comparative example 1-1;
fig. 5 shows graphs showing capacity retention rates at room temperature of lithium batteries of example 1-1 and comparative example 1-1;
fig. 6 shows graphs showing capacity retention rates at high temperatures of lithium batteries of example 1-1 and comparative example 1-1; and is also provided with
Fig. 7 shows a view of a lithium battery according to an embodiment.
Detailed Description
Exemplary embodiments will now be described more fully hereinafter with reference to the accompanying drawings; however, they may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the exemplary embodiments to those skilled in the art.
The lithium battery according to an embodiment may include: a cathode comprising a cathode active material, an anode comprising an anode active material, and an organic electrolyte solution between the cathode and the anode. The cathode may include a carbonaceous nanostructure, and the organic electrolyte solution includes a first lithium salt, an organic solvent, and a bicyclic sulfate-based compound represented by the following formula 1:
< 1>
Wherein in formula 1, A 1 、A 2 、A 3 And A 4 Each independently is a covalent bond, substituted or unsubstituted C 1 -C 5 Alkylene, carbonyl or sulfinyl, wherein A 1 And A 2 Not all are covalent bonds, and A 3 And A 4 Not all covalent bonds.
An organic electrolyte solution for a lithium battery (including a dicyclosulfate-based compound as an additive) may enhance battery performance of the lithium battery, such as high temperature characteristics, life characteristics, and the like.
In addition, since the cathode active material in the cathode includes a carbonaceous nanostructure, the high temperature life characteristics and high temperature stability of the lithium battery can be further enhanced. In addition, the impregnation of the cathode with the electrolyte solution can be enhanced.
The bicyclic sulfate-based compound may have a structure in which two sulfate rings are connected to each other in a spiro form.
Without being bound by any particular theory and for better understanding, the reason for improving the performance of lithium batteries by adding a biscyclosulfate based compound to the electrolyte solution will now be described in further detail.
When the dicyclic sulfate-based compound is included in the electrolyte solution, the sulfate group of the dicyclic sulfate-based compound may be reduced by itself by accepting electrons from the anode surface during charging, or may react with polar solvent molecules previously reduced, thereby affecting the characteristics of the SEI layer formed at the anode surface. For example, a bicyclic sulfate-based compound comprising a sulfate group may accept electrons from the anode more readily than a polar solvent. For example, the biscyclosulfate-based compound may be reduced at a lower voltage than that required for the polar solvent reduction before the polar solvent is reduced.
For example, the bicyclic sulfate-based compounds have sulfate groups and thus may be more easily reduced and/or decomposed into free radicals and/or ions during charging. As a result, the radicals and/or ions combine with lithium ions to form an appropriate SEI layer on the anode, thereby preventing the formation of products obtained by further decomposing the solvent. The bicyclic sulfate-based compound may form covalent bonds with, for example, the carbonaceous anode itself or various functional groups on the surface of the carbonaceous anode, or may be adsorbed onto the surface of the electrode. The modified SEI layer formed by such bonding and/or adsorption with improved stability can be more durable even after long-time charge and discharge, compared to an SEI layer formed only by an organic solvent. The durable modified SEI layer may instead more effectively prevent co-intercalation of organic solvents solvated lithium ions during lithium ion intercalation electrodes. Accordingly, the modified SEI layer may more effectively prevent direct contact between the organic solvent and the anode to further improve reversibility of intercalation/deintercalation of lithium ions, thereby achieving an increase in discharge capacity and an improvement in life characteristics of the fabricated battery.
In addition, since the sulfate group is included, the dicyclic sulfate-based compound may coordinate on the cathode surface, thereby affecting the characteristics of the protective layer formed on the cathode surface. For example, the sulfate group may coordinate with a transition metal ion of the cathode active material to form a complex. The complex can form a modified protective layer with improved stability, which is more durable than a protective layer formed of only an organic solvent even after long-time charge and discharge. In addition, the durable modified protective layer may more effectively prevent co-intercalation of organic solvents solvated lithium ions during intercalation of lithium ions into the electrode. Therefore, the modified protective layer can more effectively prevent direct contact between the organic solvent and the cathode to further improve reversibility of intercalation/deintercalation of lithium ions, thereby achieving improved stability and improved life characteristics of the fabricated battery.
Furthermore, the biscyclosulfate-based compound has a structure in which a plurality of rings are linked in a spiro form, and thus has a relatively larger molecular weight than the usual sulfate-based compound, and thus, may be thermally stable.
For example, the dicyclic sulfate-based compound may form an SEI layer at a protective layer of an anode surface or a cathode surface, and may exhibit enhanced lifetime characteristics of lithium batteries manufactured at high temperature due to improved thermal stability.
In the above-mentioned bicyclic sulfate-based compound of formula 1 contained in the organic electrolyte solution, A 1 、A 2 、A 3 And A 4 At least one of which may be unsubstituted or substituted C 1 -C 5 Alkylene, and substituted C 1 -C 5 The substituent of the alkylene group may be halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl or a polar functional group having at least one heteroatom.
For example, A 1 、A 2 、A 3 And A 4 At least one of which may be unsubstituted or substituted C 1 -C 5 Alkylene, and substituted C 1 -C 5 The substituent of the alkylene group may be halogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl. For example, substituted C 1 -C 5 The substituent of the alkylene group may be any suitable substituent useful for alkylene groups used in the art.
For example, in the above-described bicyclic sulfate-based compound of formula 1, substituted C 1 -C 5 The substituent of the alkylene group may be a polar functional group having a heteroatom, and the heteroatom of the polar functional group may be at least one selected from halogen, oxygen, nitrogen, phosphorus, sulfur, silicon, and boron.
For example, the polar functional group having a heteroatom may be at least one selected from the group consisting of: -F、-Cl、-Br、-I、-C(＝O)OR 16 、-OR 16 、-OC(＝O)OR 16 、-R 15 OC(＝O)OR 16 、-C(＝O)R 16 、-R 15 C(＝O)R 16 、-OC(＝O)R 16 、-R 15 OC(＝O)R 16 、-C(＝O)-O-C(＝O)R 16 、-R 15 C(＝O)-O-C(＝O)R 16 、-SR 16 、-R 15 SR 16 、-SSR 16 、-R 15 SSR 16 、-S(＝O)R 16 、-R 15 S(＝O)R 16 、-R 15 C(＝S)R 16 、-R 15 C(＝S)SR 16 、-R 15 SO 3 R 16 、-SO 3 R 16 、-NNC(＝S)R 16 、-R 15 NNC(＝S)R 16 、-R 15 N＝C＝S、-NCO、-R 15 -NCO、-NO 2 、-R 15 NO 2 、-R 15 SO 2 R 16 、-SO 2 R 16 、
In the above formula, R 11 And R is 15 May each independently be halogen substituted or unsubstituted C 1 -C 20 Alkylene, halogen substituted or unsubstituted C 2 -C 20 Alkenylene, halogen substituted or unsubstituted C 2 -C 20 Alkynylene, halogen substituted or unsubstituted C 3 -C 12 Cycloalkylene, halogen substituted or unsubstituted C 6 -C 40 Arylene, halogen substituted or unsubstituted C 2 -C 40 Heteroarylene, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl or halogen substituted or unsubstituted C 7 -C 15 An aralkylene group; and R is 12 、R 13 、R 14 And R is 16 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 12 Cycloalkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl, halogen substituted or unsubstituted C 7 -C 15 Trialkylsilyl or halogen substituted or unsubstituted C 7 -C 15 Aralkyl group, andrepresenting the binding site to an adjacent atom.
For example, in polar functional groups having heteroatoms, the halogen substituent of an alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkylaryl, trialkylsilyl or aralkyl group can be fluorine (F).
For example, the bicyclic sulfate-based compound contained in the organic electrolyte solution may be represented by formula 2 or 3:
wherein in formulas 2 and 3, B 1 、B 2 、B 3 、B 4 、D 1 And D 2 Can each independently be-C (E 1 )(E 2 ) -carbonyl or sulfinyl; and E is 1 And E is 2 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
For example, E 1 And E is 2 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 10 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
For example, E 1 And E is 2 Can each independently be hydrogen, F, chlorine (Cl), bromine (Br), iodine (I), methyl, ethyl, propyl, isopropyl, butyl, t-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl, or pyridyl.
For example, E 1 And E is 2 May each independently be hydrogen, F, methyl, ethyl, trifluoromethyl, tetrafluoroethyl or phenyl.
For example, the bicyclic sulfate-based compound may be represented by formula 4 or 5:
wherein in formula 4 and formula 5, R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
For example, in the above formulas 4 and 5, R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 Can be hydrogen, F, cl, br, I, methyl, ethyl, propyl, isopropyl, butyl, t-butyl A group, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl group.
For example, in the above formulas 4 and 5, R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 May each independently be hydrogen, F, methyl, ethyl, propyl, trifluoromethyl, tetrafluoroethyl or phenyl.
Specifically, the biscyclosulfate-based compound may be represented by one of the following formulas 6 to 17:
as used herein, the expression "C a -C b "a and b represent the number of carbon atoms of a particular functional group. For example, the functional group may include a to b carbon atoms. For example, the expression "C 1 -C 4 Alkyl "means an alkyl group having 1 to 4 carbon atoms, i.e. CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 CH 2 CH 2 CH 2 -、CH 3 CH 2 CH(CH 3 ) -and (CH) 3 ) 3 C-。
Depending on the context, a particular group may be referred to as a monovalent group or a divalent group. For example, a substituent may be understood as a divalent group when it requires two binding sites for binding to the rest of the molecule. For example, the substituents designated as alkyl groups requiring two binding sites may be divalent groups, e.g., -CH 2 -、-CH 2 CH 2 -、-CH 2 CH(CH 3 )CH 2 -and the like. The term "alkylene" as used herein explicitly indicates that the group is a divalent group.
The terms "alkyl" and "alkylene" as used herein refer to a branched or unbranched aliphatic hydrocarbon group. In one embodiment, the alkyl group may be substituted or unsubstituted. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl, wherein each of these groups may be optionally substituted or unsubstituted. In one embodiment, the alkyl group may have 1 to 6 carbon atoms. For example, C 1 -C 6 Alkyl groups can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, 3-pentyl, hexyl, and the like.
The term "cycloalkyl" as used herein means a fully saturated carbocyclic ring or ring system. For example, cycloalkyl groups may be cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The term "alkenyl" as used herein refers to a hydrocarbon group having 2 to 20 carbon atoms and having at least one carbon-carbon double bond. Examples of alkenyl groups include vinyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl. In one embodiment, these alkenyl groups may be substituted or unsubstituted. In one embodiment, alkenyl groups may have 2 to 40 carbon atoms.
The term "alkynyl" as used herein refers to a hydrocarbon group having 2 to 20 carbon atoms and having at least one carbon-carbon triple bond. Examples of alkynyl groups include ethynyl, 1-propynyl, 1-butynyl and 2-butynyl. In one embodiment, these alkynyl groups may be substituted or unsubstituted. In one embodiment, alkynyl groups may have 2 to 40 carbon atoms.
The term "aromatic" as used herein refers to a ring or ring system having a conjugated pi electron system, and may refer to carbocyclic aromatic groups (e.g., phenyl) and heterocyclic aromatic groups (e.g., pyridine). In this regard, the aromatic ring system as a whole may comprise a single ring or a fused multiple ring (i.e., rings sharing adjacent pairs of atoms).
The term "aryl" as used herein refers to an aromatic ring or ring system having only carbon atoms in its backbone (i.e., rings fused by at least two rings sharing two adjacent carbon atoms). When aryl is a ring system, each ring in the ring system is aromatic. Examples of aryl groups include phenyl, biphenyl, naphthyl, phenanthryl, and tetracenyl. These aryl groups may be substituted or unsubstituted.
The term "heteroaryl" as used herein refers to an aromatic ring system having one ring or multiple fused rings, wherein at least one ring atom is not carbon, i.e., a heteroatom. In a fused ring system, at least one heteroatom may be present in only one ring. For example, the heteroatom may be oxygen, sulfur or nitrogen. Examples of heteroaryl groups include furyl, thienyl, imidazolyl, quinazolinyl, quinolinyl, isoquinolinyl, quinoxalinyl, pyridyl, pyrrolyl, oxazolyl and indolyl.
The terms "aralkyl" and "alkylaryl" as used herein refer to an aryl group attached as a substituent through an alkylene group, e.g., C 7 -C 14 Aralkyl groups. Examples of aralkyl or alkylaryl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and naphthylalkyl. In one embodiment, the alkylene may be a lower alkylene (i.e., C 1 -C 4 An alkylene group).
The term "cycloalkenyl" as used herein refers to a non-aromatic carbocyclic ring or ring system having at least one double bond. For example, the cycloalkenyl group may be cyclohexenyl.
The term "heterocyclyl" as used herein refers to a non-aromatic ring or ring system having at least one heteroatom in its ring backbone.
The term "halogen" as used herein refers to a stable element belonging to group 17 of the periodic table of elements, such as fluorine, chlorine, bromine or iodine. For example, halogen may be fluorine and/or chlorine.
In this specification, a substituent may be obtained by substituting at least one hydrogen atom in an unsubstituted parent group with another atom or functional group. The term "substituted" means that the functional group listed above is substituted with at least one substituent selected from the group consisting of: c (C) 1 -C 40 Alkyl, C 2 -C 40 Alkenyl group,C 3 -C 40 Cycloalkyl, C 3 -C 40 Cycloalkenyl and C 7 -C 40 Aryl groups. The phrase "optionally substituted" as used herein means that the above functional groups may be substituted with the above substituents or may be unsubstituted.
The amount of the bicyclic sulfate-based compound of formula 1 as an additive in the organic electrolyte solution may be in the range of about 0.4wt% to about 5wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.4wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.5wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.6wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.7wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.4wt% to about 2.5wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.4wt% to about 2wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.4wt% to about 1.5wt% based on the total weight of the organic electrolyte solution. When the amount of the biscyclosulfate based compound of formula 1 is within the above range, further enhanced battery characteristics can be obtained.
The first lithium salt included in the organic electrolyte solution may include at least one selected from the group consisting of: liPF (LiPF) 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiClO 4 、LiCF 3 SO 3 、Li(CF 3 SO 2 ) 2 N、LiC 4 F 9 SO 3 、LiAlO 2 、LiAlCl 4 、LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) (wherein x is more than or equal to 2 and less than or equal to 20, and y is more than or equal to 2 and less than or equal to 20), liCl and LiI.
The concentration of the first lithium salt in the organic electrolyte solution may be, for example, about 0.01M to about 2.0M. The concentration of the first lithium salt in the organic electrolyte solution may be appropriately adjusted as needed. When the concentration of the first lithium salt is within the above range, a battery having further enhanced characteristics can be obtained.
The organic solvent contained in the organic electrolyte solution may be a low boiling point solvent. By low boiling point solvent is meant a solvent having a boiling point of 200 ℃ or less at 25 ℃ at 1 atmosphere.
For example, the organic solvent may include at least one selected from the group consisting of: dialkyl carbonates, cyclic carbonates, linear or cyclic esters, linear or cyclic amides, alicyclic nitriles, linear or cyclic ethers and derivatives thereof.
For example, the organic solvent may include at least one selected from the group consisting of: dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), methylpropyl carbonate, ethylpropyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, propylene Carbonate (PC), ethylene Carbonate (EC), butylene carbonate, ethyl propionate, ethyl butyrate, acetonitrile, succinonitrile (SN), dimethyl sulfoxide, dimethylformamide, dimethylacetamide, gamma valerolactone, gamma butyrolactone and tetrahydrofuran. For example, the organic solvent may be any suitable solvent available in the art having a low boiling point.
In addition to the bicyclic sulfate-based compound, the organic electrolyte solution may further comprise other additives. By further including other additives, a lithium battery having further enhanced performance can be obtained.
Additives further included in the organic electrolyte solution may include cyclic carbonate compounds, second lithium salts, and the like.
For example, the organic electrolyte solution may further contain a cyclic carbonate compound as an additive. The cyclic carbonate compound used as an additive may be selected from vinylene carbonates(VC); is selected from halogen, cyano (-CN) and nitro (-NO) 2 ) VC substituted by at least one substituent of (a); vinyl Ethylene Carbonate (VEC); selected from halogen, -CN and-NO 2 VEC substituted by at least one substituent of (C); fluoroethylene carbonate (FEC); is selected from halogen, -CN and-NO 2 FEC substituted by at least one substituent of (a). When the organic electrolyte solution further contains a cyclic carbonate compound as an additive, a lithium battery containing the organic electrolyte solution may have further enhanced charge and discharge characteristics.
The amount of cyclic carbonate compound in the organic electrolyte solution may be, for example, about 0.01wt% to about 5wt% based on the total weight of the organic electrolyte solution. The amount of the cyclic carbonate compound may be appropriately adjusted as needed. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.1wt% to about 5wt% based on the total weight of the organic electrolyte solution. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.1wt% to about 4wt% based on the total weight of the organic electrolyte solution. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.1wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.1wt% to about 2wt% based on the total weight of the organic electrolyte solution. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.2wt% to about 2wt% based on the total weight of the organic electrolyte solution. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.2wt% to about 1.5wt% based on the total weight of the organic electrolyte solution. When the amount of the cyclic carbonate compound is within the above range, a battery having further enhanced characteristics can be obtained.
For example, the organic electrolyte solution may further include a second lithium salt as an additive. The second lithium salt is different from the first lithium salt, and its anion can be oxalate, PO 2 F 2 - 、N(SO 2 F) 2 - Etc. For example, the second lithium salt may be a compound represented by one of the following formulas 18 to 25:
the amount of the second lithium salt in the organic electrolyte solution may be, for example, about 0.1wt% to about 5wt% based on the total weight of the organic electrolyte solution. The amount of the second lithium salt may be appropriately adjusted as needed. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.1wt% to about 4.5wt% based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.1wt% to about 4wt% based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.1wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.1wt% to about 2wt% based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.2wt% to about 2wt% based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.2wt% to about 1.5wt% based on the total weight of the organic electrolyte solution. When the amount of the second lithium salt is within the above range, a battery having further enhanced characteristics can be obtained.
The organic electrolyte solution may be in a liquid or gel state. The organic electrolyte solution may be prepared by adding the above-described first lithium salt and an additive to the above-described organic solvent.
The carbonaceous nanostructure included in the cathode of the lithium battery may be at least one selected from the group consisting of a one-dimensional carbonaceous nanostructure and a two-dimensional carbonaceous nanostructure. For example, the carbonaceous nanostructure may be a Carbon Nanotube (CNT), a carbon nanofiber, graphene nanoplatelets, hollow carbon, porous carbon, mesoporous carbon, or the like.
The carbonaceous nanostructures may have a length of about 1 μm to about 180 μm, 1 μm to about 200 μm, about 2 μm to about 160 μm, about 3 μm to about 140 μm, about 4 μm to about 120 μm, or about 5 μm to about 100 μm. When the length of the carbonaceous nanostructure is within the above range, the life characteristics and high temperature stability of the lithium battery may be further enhanced. The term "length of a carbonaceous nanostructure" as used herein refers to the maximum value of the distance between the opposite ends of a plurality of carbonaceous nanostructures. In the present specification, the term "average length" of a carbonaceous nanostructure refers to a calculated average of the lengths of a plurality of carbonaceous nanostructures.
The amount of carbonaceous nanostructures included in the cathode of the lithium battery may range from about 0.5wt% to about 5wt%, from about 0.5wt% to about 3wt%, from about 0.5wt% to about 2.5wt%, from about 0.5wt% to about 2wt%, or from about 0.5wt% to about 1.5wt%, based on the total weight of the cathode mixture. When the amount of the carbonaceous nanostructure is within the above range, the impregnation of the cathode into the electrolyte solution may be further enhanced. Due to the enhanced impregnation property, the electrolyte solution is uniformly distributed in the cathode, and thus side reactions between the cathode and the electrolyte solution are suppressed. Accordingly, the lithium battery including the electrolyte solution having enhanced impregnation property has reduced internal resistance, and as a result, cycle characteristics of the lithium battery are enhanced. In addition, since the time taken to assemble the lithium battery is shortened due to the enhanced impregnation, the productivity is improved in the manufacturing process of the lithium battery.
Examples of the types of lithium batteries include lithium secondary batteries (such as lithium ion batteries, lithium ion polymer batteries, lithium sulfur batteries, and the like), and lithium primary batteries.
For example, in a lithium battery, the anode may include graphite. For example, in a lithium battery, the cathode may include a nickel-containing layered lithium transition metal oxide. For example, a lithium battery may have a high voltage of about 3.80V or higher. For example, a lithium battery may have a high voltage of about 4.0V or higher. For example, a lithium battery may have a high voltage of about 4.35V or higher.
The nickel-containing layered lithium transition metal oxide contained in the cathode of the lithium battery is represented by, for example, the following formula 26:
< 26>
Li a Ni x Co y M z O 2-b A b
Wherein in formula 26, a is 1.0.ltoreq.a.ltoreq.1.2, b is 0.ltoreq. 0.2,0.6.ltoreq.x <1,0< y is 0.2,0< z is 0.2, and x+y+z=1; m is at least one selected from manganese (Mn), vanadium (V), magnesium (Mg), gallium (Ga), silicon (Si), tungsten (W), molybdenum (Mo), iron (Fe), chromium (Cr), copper (Cu), zinc (Zn), titanium (Ti), aluminum (Al) and boron (B); and A is fluorine (F), sulfur (S), chlorine (Cl), bromine (Br), or a combination thereof. For example, 0.7.ltoreq.x <1,0< y.ltoreq.0.15, 0< z.ltoreq.0.15, and x+y+z=1. For example, 0.75.ltoreq.x <1,0< y.ltoreq.0.125, 0< z.ltoreq.0.125, and x+y+z=1. For example, 0.8.ltoreq.x <1,0< y.ltoreq.0.1, 0< z.ltoreq.0.1, and x+y+z=1. For example, 0.85.ltoreq.x <1,0< y.ltoreq.0.075, 0< z.ltoreq.0.075, and x+y+z=1.
The nickel-containing layered lithium transition metal oxide contained in the cathode of the lithium battery is represented by, for example, formula 27 or formula 28:
< 27>
LiNi x Co y Mn z O 2
< 28>
LiNi x Co y Al z O 2
Wherein in the formulas 27 and 28, 0.6.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.2, 0< z.ltoreq.0.2, and x+y+z=1. For example, 0.7.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.15, 0< z.ltoreq.0.15, and x+y+z=1. For example, 0.75.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.125, 0< z.ltoreq.0.125, and x+y+z=1. For example, 0.8.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.1, 0< z.ltoreq.0.1, and x+y+z=1. For example, 0.85.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.075, 0< z.ltoreq.0.075, and x+y+z=1.
For example, a lithium battery can be manufactured using the following method.
The cathode may be prepared by a suitable method. For example, a cathode active material composition is prepared in which a cathode active material, a conductive material, a binder, and a solvent are mixed. The cathode active material composition may be directly coated onto a metal current collector, thereby completing the fabrication of a cathode plate. In another embodiment, the cathode active material composition may be cast onto a separate support, and a film separated from the support may be laminated onto a metal current collector, thereby completing the fabrication of the cathode plate.
The cathode active material may be a suitable lithium-containing metal oxide used in the art. For example, the cathode active material may be a compound represented by any one of the following formulas: li (Li) a A 1-b B' b D 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0 and less than or equal to 0.5; li (Li) a E 1-b B' b O 2-c D c Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05; liE 2-b B' b O 4-c D c Wherein b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05; li (Li) a Ni 1-b-c Co b B' c D α Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α≤2；Li a Ni 1-b-c Co b B' c O 2-α F' α Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；Li a Ni 1-b- c Co b B' c O 2-α F' 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；Li a Ni 1-b-c Mn b B' c D α Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α≤2；Li a Ni 1-b-c Mn b B' c O 2-α F' α Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；Li a Ni 1-b-c Mn b B' c O 2-α F' 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；Li a Ni b E c G d O 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, and d is more than or equal to 0.001 and less than or equal to 0.1; li (Li) a Ni b Co c Mn d G e O 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, d is more than or equal to 0 and less than or equal to 0.5, and e is more than or equal to 0.001 and less than or equal to 0.1; li (Li) a NiG b O 2 Wherein 0.90.ltoreq.a.ltoreq.1.8 and 0.001.ltoreq.b.ltoreq.0.1; li (Li) a CoG b O 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.1; li (Li) a MnG b O 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.1; li (Li) a Mn 2 G b O 4 Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.1; QO (quality of service) 2 ；QS 2 ；LiQS 2 ；V 2 O 5 ；LiV 2 O 5 ；LiI'O 2 ；LiNiVO 4 ；Li (3-f) J 2 (PO 4 ) 3 Wherein f is more than or equal to 0 and less than or equal to 2; li (Li) (3-f) Fe 2 (PO 4 ) 3 Wherein f is more than or equal to 0 and less than or equal to 2; liFePO 4 . The cathode mixture may include substances other than a solvent for forming a cathode active material slurry, for example, it may include a cathode active material, a conductive material, and a binder.
In the above formula, A may be selected from nickel (Ni), cobalt (Co), manganese (Mn), and combinations thereof; b' may be selected from aluminum (Al), ni, co, manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), rare earth elements, and combinations thereof; d may be selected from oxygen (O), fluorine (F), sulfur (S), phosphorus (P), and combinations thereof; e may be selected from Co, mn, and combinations thereof; f' may be selected from F, S, P and combinations thereof; g may be selected from Al, cr, mn, fe, mg, lanthanum (La), cerium (Ce), sr, V, and combinations thereof; q may be selected from titanium (Ti), molybdenum (Mo), mn, and combinations thereof; i' may be selected from Cr, V, fe, scandium (Sc), yttrium (Y), and combinations thereof; j may be selected from V, cr, mn, co, ni, copper (Cu) and combinations thereof.
For example, the cathode active material may be LiCoO 2 、LiMn x O 2x Wherein x=1 or 2; liNi 1-x Mn x O 2x Wherein 0 is<x<1；LiNi 1-x-y Co x Mn y O 2 Wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 0 and less than or equal to 0.5; liFePO 4 Etc. In another embodiment, the cathode active material may preferably include, for example, a polymer represented by formula 26: li (Li) a Ni x Co y M z O 2-b A b Represented are nickel-containing layered lithium transition metal oxides.
In addition, the above-mentioned lithium-containing metal oxide used as a cathode active material may have a coating layer on the surface thereof. In another embodiment, a mixture of a lithium-containing metal oxide and a lithium-containing metal oxide having a coating on its surface may be used. The coating may comprise a coating element compound, such as an oxide of a coating element, a hydroxide of a coating element, a oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element. The coating element compound may be amorphous or crystalline. The coating element included in the coating layer may be selected from Mg, al, co, potassium (K), sodium (Na), calcium (Ca), silicon (Si), ti, V, tin (Sn), germanium (Ge), gallium (Ga), boron (B), arsenic (As), zirconium (Zr), and mixtures thereof. The coating layer may be formed by using any one of various methods (e.g., spraying, dipping, etc.) that do not adversely affect the physical properties of the cathode active material, by using the coating element in the above-described compound. The coating forming method is obvious to those of ordinary skill in the art, and thus a detailed description thereof will not be provided herein.
Suitable conductive substances may be used. The conductive material may be, for example, carbon black, graphite particles, and the like.
The adhesive may be a suitable adhesive used in the art. Examples of binders include vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene, mixtures thereof, and styrene butadiene rubber based polymers.
The solvent may be, for example, N-methylpyrrolidone, acetone, water, etc.
The amounts of the cathode active material, the conductive material, the binder, and the solvent may be the same as those used in a general lithium battery. Depending on the intended use and configuration of the lithium battery, at least one of a conductive substance, a binder, and a solvent may not be used.
Anodes can be prepared by suitable manufacturing methods. For example, the anode active material composition is prepared by mixing an anode active material, a conductive material, a binder, and a solvent. The anode active material composition may be directly coated on a metal current collector and dried to obtain an anode plate. In some embodiments, the anode active material composition may be cast onto a separate support, and a film separate from the support may be laminated onto a metal current collector to complete the fabrication of the anode plate.
As the anode active material, any anode active material of a lithium battery used in the art may be used. For example, the anode active material may include at least one selected from lithium metal, metal that can alloy with lithium, transition metal oxide, non-transition metal oxide, and carbonaceous material.
For example, the metal that can be alloyed with lithium may be Si, sn, al, ge, lead (Pb), bismuth (Bi), antimony (Sb), si-Y 'alloys (Y' is an alkali metal, alkaline earth metal, group 13 and 14 element, transition metal, rare earth element, or a combination thereof, and is not Si), sn-Y 'alloys (Y' is an alkali metal, alkaline earth metal, group 13 and 14 element, transition metal, rare earth element, or a combination thereof, and is not Sn), and the like. The element Y' may be selected from Mg, ca, sr, ba, radium (Ra), sc, Y, ti, zr, hafnium (Hf),(Rf), V, niobium (Nb), tantalum (Ta)>(Db), cr, mo, tungsten (W), and (B)>(Sg), technetium (Tc), rhenium (Re)>(Bh), fe, pb, ruthenium (Ru), osmium (Os), -, and the like>(Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), cu, silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), B, al, ga, sn, indium (In), ge, P, as, sb, bi, S, selenium (Se), tellurium (Te), polonium (Po), and combinations thereof.
For example, the transition metal oxide may be lithium titanium oxide, vanadium oxide, lithium vanadium oxide, or the like.
For example, the non-transition metal oxide may be SnO 2 、SiO x (wherein 0<x<2) Etc.
For example, the carbonaceous material may be crystalline carbon, amorphous carbon, or mixtures thereof. Examples of the crystalline carbon include natural graphite and artificial graphite, each of which has an irregular shape or is in the form of a plate, a sheet, a sphere, or a fiber. Examples of amorphous carbon include soft carbon (low temperature calcined carbon), hard carbon, mesophase pitch carbonized products, and calcined coke.
In the anode active material composition, the same conductive material and binder as those used in the cathode active material composition may be used.
The amounts of the anode active material, the conductive material, the binder, and the solvent may be the same as those used in a general lithium battery. Depending on the intended use and configuration of the lithium battery, at least one of a conductive substance, a binder, and a solvent may not be used.
A suitable separator to be disposed between the cathode and the anode may be prepared. As the separator, a separator having low resistance to ion migration in the electrolyte and high electrolyte holding capacity can be used. Examples of separators may include fiberglass, polyester, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and combinations thereof, each of which may be a nonwoven or woven fabric. For example, a rollable separator formed of polyethylene, polypropylene, or the like may be used for a lithium ion battery, and a separator having a high organic electrolyte solution retaining ability may be used for a lithium ion polymer battery. For example, the separator may be manufactured according to the following method.
The polymer resin, filler, and solvent may be mixed together to prepare the separator composition. The separator composition may then be coated directly on the electrode and dried to form a separator. In another embodiment, the separator composition may be cast on a support and dried, and then a separator film separated from the support may be laminated on an upper portion of the electrode, thereby completing the manufacture of the separator.
Suitable materials for the binder of the electrode plate may be used to manufacture the separator. For example, the polymer resin may be vinylidene fluoride/hexafluoropropylene copolymer, PVDF, polyacrylonitrile, polymethyl methacrylate, mixtures thereof, and the like.
The above-mentioned organic electrolyte solution may be prepared.
As shown in fig. 7, the lithium battery 1 includes a cathode 3, an anode 2, and a separator 4. The cathode 3, the anode 2, and the separator 4 are wound or folded and then accommodated in the battery case 5. Subsequently, an organic electrolyte solution is injected into the battery case 5, and the battery case 5 is sealed with the cap assembly 6, thereby completing the manufacture of the lithium battery 1. The battery case 5 may have a cylindrical, rectangular or film shape.
A separator 4 may be disposed between the cathode 3 and the anode 2 to form a battery assembly. Multiple battery assemblies may be stacked into a double battery structure and impregnated with an organic electrolyte solution, and the resultant placed in a pouch and sealed, thereby completing the fabrication of a lithium battery.
The battery assemblies may be stacked to form a battery pack. Such a battery pack may be used in devices requiring high capacity and high power output. For example, the battery pack may be used for a notebook computer, a smart phone, an electric vehicle, and the like.
The lithium battery may have excellent life characteristics and high rate characteristics, and thus may be used for an Electric Vehicle (EV). For example, lithium batteries may be used in hybrid vehicles, such as plug-in hybrid electric vehicles (PHEVs), and the like. Lithium batteries are also used in fields where a large amount of electricity needs to be stored. For example, lithium batteries may be used in electric bicycles, motor driven tools, and the like.
The following examples and comparative examples are provided to highlight features of one or more embodiments, but it should be understood that the examples and comparative examples should not be construed as limiting the scope of the embodiments nor as being outside the scope of the embodiments. Furthermore, it should be understood that the embodiments are not limited to the specific details described in the examples and comparative examples.
Synthesis of additives
Preparation example 1: synthesis of Compound of formula 6
The compound of formula 6 can be prepared according to the following reaction scheme 1:
reaction scheme 1
Synthesis of Compound A
68.0g (0.499 mol) of pentaerythritol and 100g of molecular sieve (type 4A) were added to a volume ratio of 1:1 of Tetrahydrofuran (THF) and dichloromethane (DCM, CH) 2 Cl 2 ) And the resulting solution was refluxed for 20 minutes. Subsequently, 110ml (2.8 eq, 1.40 mol) of thionyl chloride (SOCl) 2 ) To the resultant was added and the resulting solution was refluxed for 8 hours until pentaerythritol was completely consumed by the reaction, thereby obtaining a pale yellow solution. The resulting pale yellow solution was filtered and concentrated to give a residue containing a pale yellow solid. Thereafter, 1L of saturated sodium bicarbonate (NaHCO) 3 ) The solution is added directly to the residue at a rate that minimizes effervescence to give a suspension. The suspension was vigorously stirred for 20 minutes. Then, the suspension was filtered, and the resulting solid was added to 1L of purified water to prepare a mixture. Then, the mixture was vigorously stirred for 20 minutes, suction filtered, and dried in air, to give 104.61g (0.458 mol) of Compound A (yield: 92%).
Compound A 1 H-NMR 13 The C-NMR data are the same as in the literature.
Synthesis of Compound B
As shown in the above reaction scheme 1, compound B represented by the following formula 6 was synthesized from compound a according to the method disclosed in Canadian Journal of Chemistry,79,2001, page 1042.
The synthesized compound was recrystallized in a mixed solvent of 1, 2-dichloroethane and acetonitrile in a volume ratio of 2:1, and then used for preparing an electrolyte solution.
< 6>
Preparation of organic electrolyte solution
Example 1: SEI-1316.0 wt%
0.90M LiPF as lithium salt 6 And 1wt% of a compound of formula 6 to a 3:5:2 by volume ratio of subcarbonateEthyl Ester (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) to prepare an organic electrolyte solution.
< 6>
Example 2: SEI-1316.0wt% +VC 0.5wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that 1wt% of the compound of formula 6 and 0.5wt% of Vinylene Carbonate (VC) were used as additives.
Example 3: SEI-1316.5 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 0.5 wt%.
Example 8: SEI-1316 2wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 2 wt%.
Example 9: SEI-1316 3wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 as an additive was changed to 3 wt%.
Example 9a: SEI-1316 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 as an additive was changed to 4 wt%.
Example 10: SEI-1316 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 as an additive was changed to 5 wt%.
Comparative example 1: SEI-1316 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the compound of formula 6 was not used as an additive.
Lithium battery production (examples 1-1 to 3-1 and comparative example 1-1)
Example 1-1
Manufacture of anode
98wt% of artificial graphite (BSG-L manufactured by Tianjin BTR New Energy Technology co., ltd.) as a binder, 1.0wt% of styrene-butadiene rubber (SBR) (manufactured by Zeon) and 1.0wt% of carboxymethyl cellulose (CMC) (manufactured by NIPPON a & L) were mixed together, the mixture was added to distilled water, and the resulting solution was stirred using a mechanical stirrer for 60 minutes to prepare an anode active material slurry. The anode active material slurry was coated onto a copper (Cu) current collector having a thickness of 10 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 ℃ for 0.5 hours, followed by further drying under the following conditions: the fabrication of the anode plate was completed by performing vacuum at 120 deg.c for 4 hours and rolling.
Cathode fabrication
97.45wt% of LiNi 1/3 Co 1/3 Mn 1/3 O 2 0.5wt% of powdered artificial graphite (SFG 6 manufactured by Timcal), 0.7wt% of carbon black (Ketjen black manufactured by ECP), 0.25wt% of modified acrylonitrile rubber (BM-720H manufactured by Zeon Corporation), 0.9wt% of polyvinylidene fluoride (PVDF, S6020 manufactured by Solvay) and 0.2wt% of PVDF (S5130 manufactured by Solvay) as a conductive substance were mixed together, and the mixture was added to N-methyl-2-pyrrolidone as a solvent, and the resulting solution was stirred using a mechanical stirrer for 30 minutes to prepare a cathode active material slurry. The cathode active material slurry was coated onto an aluminum (Al) current collector having a thickness of 20 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 ℃ for 0.5 hours, followed by further drying under the following conditions: the production of the cathode plate was completed by performing vacuum at 120℃for 4 hours and rolling.
A polyethylene separator having a thickness of 14 μm was used, the cathode side of which was coated with ceramic, and the organic electrolyte solution prepared according to example 1 was used to complete the fabrication of a lithium battery.
Examples 2-1 and 3-1
A lithium battery was fabricated in the same manner as in example 1-1, except that the organic electrolyte solutions prepared according to examples 2 and 3 were used instead of the organic electrolyte solution of example 1, respectively.
Comparative example 1-1
A lithium battery was fabricated in the same manner as in example 1-1, except that the organic electrolyte solution prepared according to comparative example 1 was used instead of the organic electrolyte solution of example 1.
Evaluation example 1: evaluation of charge and discharge characteristics at 4.25V and at room temperature (25 ℃ C.)
The lithium batteries manufactured according to examples 1-1 to 3-1 and comparative example 1-1 were each charged at 25 ℃ with a constant current at 0.1C rate until the voltage reached 4.25V (relative to Li), and then the charging process was cut off with a current at 0.05C rate while maintaining a constant voltage of 4.25V. Subsequently, each lithium battery was discharged with a constant current of 0.1C magnification until the voltage reached 2.8V (with respect to Li) (forming operation, first cycle).
Each lithium battery after the first cycle of the forming operation was charged at 25 ℃ with a constant current of 0.2C rate until the voltage reached 4.25V (relative to Li), and then the charging process was cut off with a current of 0.05C rate while maintaining a constant voltage of 4.25V. Subsequently, each lithium battery was discharged with a constant current of 0.2C magnification until the voltage reached 2.8V (with respect to Li) (forming operation, second cycle).
Each lithium battery after the second cycle of the forming operation was charged at 25 ℃ with a constant current at a rate of 1.0C until the voltage reached 4.25V (relative to Li), and then the charging process was cut off with a current at a rate of 0.05C while maintaining a constant voltage of 4.25V. Subsequently, each lithium battery was discharged at a constant current of 1.0C magnification until the voltage reached 2.75V (with respect to Li), and the charge and discharge cycle was repeated 380 times.
In all charge and discharge cycles, there was a rest time of 10 minutes at the end of each charge/discharge cycle.
A part of the charge and discharge experimental results are shown in table 1 below and in fig. 1 and 2. The capacity retention rate of the 380 th cycle is defined using equation 1 below:
equation 1
Capacity retention = [ 380 th cycle discharge capacity/1 st cycle discharge capacity ] ×100
TABLE 1
Discharge capacity [ mAh/g of 380 th cycle] Capacity retention [%]
Example 1-1 202 75
Example 2-1 228 82
Comparative example 1-1 173 63
As shown in table 1 and fig. 1 and 2, the lithium batteries of examples 1-1 and 2-1, which included additives according to embodiments of the present disclosure, exhibited significantly enhanced discharge capacity and life characteristics at room temperature as compared to the lithium battery of comparative example 1-1, which did not include such additives.
Evaluation example 2: evaluation of charge and discharge characteristics at 4.25V and high temperature (45 ℃ C.)
The charge and discharge characteristics of the lithium batteries of examples 1-1 to 3-1 and comparative example 1-1 were evaluated using the same method as that used in evaluation example 1, except that the charge and discharge temperature was changed to 45 ℃. Meanwhile, the number of charge and discharge cycles was changed to 200 cycles.
A portion of the charge and discharge experimental results are shown in table 2 below and in fig. 3 and 4. The capacity retention rate of the 200 th cycle is defined using the following equation 2:
Equation 2
Capacity retention = [ discharge capacity at 200 th cycle/discharge capacity at 1 st cycle ] ×100
TABLE 2
Discharge capacity [ mAh/g of 200 th cycle] Capacity retention [%]
Example 1-1 249 83
Example 2-1 255 84
Comparative example 1-1 235 79
As shown in table 2 and fig. 3 and 4, the lithium batteries of examples 1-1 and 2-1 including the additive according to the embodiment of the present disclosure exhibited significantly enhanced discharge capacity and life characteristics at high temperature as compared to the lithium battery of comparative example 1-1 without such additive.
Evaluation example 3: evaluation of charge and discharge characteristics at 4.30V and at room temperature (25 ℃ C.)
The lithium batteries of example 1-1 and comparative example 1-1 were each charged at 25 ℃ with a constant current at 0.1C rate until the voltage reached 4.30V (relative to Li), and then the charging process was cut off with a current at 0.05C rate while maintaining a constant voltage of 4.30V. Subsequently, each lithium battery was discharged with a constant current of 0.1C magnification until the voltage reached 2.8V (with respect to Li) (forming operation, first cycle).
Each lithium battery after the first cycle of the forming operation was charged at 25 ℃ with a constant current of 0.2C rate until the voltage reached 4.30V (relative to Li), and then the charging process was cut off with a current of 0.05C rate while maintaining a constant voltage of 4.30V. Subsequently, each lithium battery was discharged with a constant current of 0.2C magnification until the voltage reached 2.8V (with respect to Li) (forming operation, second cycle).
Each lithium battery after the second cycle of the forming operation was charged at 25 ℃ with a constant current at 0.5C rate until the voltage reached 4.30V (relative to Li), and then the charging process was cut off with a current at 0.05C rate while maintaining a constant voltage of 4.30V. Subsequently, each lithium battery was discharged at a constant current of 1.0C magnification until the voltage reached 2.75V (with respect to Li), and the charge and discharge cycle was repeated 250 times.
In all charge and discharge cycles, there was a rest time of 10 minutes at the end of each charge/discharge cycle.
A part of the charge and discharge test results are shown in table 3 below and fig. 5. The capacity retention rate of the 250 th cycle is defined using the following equation 3:
equation 3
Capacity retention = [ discharge capacity of 250 th cycle/discharge capacity of 1 st cycle ] ×100
TABLE 3 Table 3
Discharge capacity [ mAh/g of 250 th cycle] Capacity retention [%]
Example 1-1 171 84
Comparative example 1-1 154 77
As shown in table 3 and fig. 5, the lithium battery of example 1-1 including the additive according to the embodiment of the present disclosure exhibited significantly enhanced discharge capacity and life characteristics at room temperature as compared to the lithium battery of comparative example 1-1 not including such additive.
Evaluation example 4: evaluation of charge and discharge characteristics at 4.30V and high temperature (45 ℃ C.)
The charge and discharge characteristics of the lithium batteries of example 1-1 and comparative example 1-1 were evaluated using the same method as that used in evaluation example 3, except that the charge and discharge temperature was changed to 45 ℃. And, the number of charge and discharge cycles was changed to 200 cycles.
A part of the charge and discharge test results are shown in table 4 below and fig. 6. The capacity retention rate of the 200 th cycle is defined using the following equation 4:
equation 4
Capacity retention = [ discharge capacity at 200 th cycle/discharge capacity at 1 st cycle ] ×100
TABLE 4 Table 4
Discharge capacity [ mAh/g of 200 th cycle] Capacity retention [%]
Example 1-1 189 90
Comparative example 1-1 174 84
As shown in table 4 and fig. 6, the lithium battery of example 1-1 including the additive according to the embodiment of the present disclosure exhibited significantly enhanced discharge capacity and life characteristics at high temperature as compared to the lithium battery of comparative example 1-1 not including such additive.
Evaluation example 5: evaluation of high temperature (60 ℃ C.) stability
The lithium batteries of examples 1-1 to 3-1 and comparative example 1-1 were subjected to first charge and discharge cycles as follows. Each lithium battery was charged at 25C with a constant current of 0.5C rate until the voltage reached 4.3V, then, while maintaining a constant voltage of 4.3V, each lithium battery was charged until the current reached 0.05C, and then discharged with a constant current of 0.5C rate until the voltage reached 2.8V.
Each lithium battery was subjected to a second charge and discharge cycle as follows. Each lithium battery was charged with a constant current of 0.5C rate until the voltage reached 4.3V, then, each lithium battery was charged until the current reached 0.05C while maintaining a constant voltage of 4.3V, and then discharged with a constant current of 0.2C rate until the voltage reached 2.8V.
A third charge and discharge cycle was performed for each lithium battery as follows. Each lithium battery was charged with a constant current of 0.5C rate until the voltage reached 4.3V, then, each lithium battery was charged until the current reached 0.05C while maintaining a constant voltage of 4.3V, and then discharged with a constant current of 0.2C rate until the voltage reached 2.80V. The discharge capacity at the 3 rd cycle was regarded as the standard capacity.
A fourth charge and discharge cycle was performed for each lithium battery as follows. Each lithium battery was charged at 0.5C rate until the voltage reached 4.30V, then, each lithium battery was charged until the current reached 0.05C while maintaining a constant voltage of 4.30V, the charged battery was stored in an oven at 60℃ for 10 days and 30 days, then, the battery was taken out of the oven, and then discharged at 0.1C rate until the voltage reached 2.80V.
A part of the charge and discharge evaluation results are shown in table 5 below. The capacity retention after high temperature storage is defined using the following equation 5:
equation 5
Capacity retention after high temperature storage [% ] = [ high temperature discharge capacity at 4 th cycle/standard capacity ] ×100 (herein, standard capacity is discharge capacity at 3 rd cycle)
TABLE 5
Capacity retention [%] Capacity retention [%]
Example 3-1 91 87
Comparative example 1-1 90 86
As shown in table 5, the lithium battery of example 3-1 including the organic electrolyte solution according to the embodiment of the present disclosure exhibited significantly enhanced high temperature stability compared to the lithium battery of comparative example 1-1 not including the organic electrolyte solution of the present invention.
Evaluation example 6: evaluation of direct-current internal resistance (DC-IR) after high-temperature (60 ℃ C.) storage
DC-IR of each lithium battery of examples 1-1 to 3-1 and comparative example 1-1 was measured at room temperature (25 ℃) before being placed in an oven at 60 ℃, after being stored in an oven at 60 ℃ for 10 days, and after being stored in an oven at 60 ℃ for 30 days, using the following methods.
Each lithium battery was subjected to a first charge and discharge cycle as follows. Each lithium battery was charged at a current of 0.5C until the voltage reached 50% soc (state of charge), the charging process was cut off at 0.02C, and then each lithium battery was left to stand for 10 minutes. Subsequently, the following treatments were performed for each lithium battery: discharging for 30 seconds at a constant current of 0.5C, then standing for 30 seconds, and charging for 30 seconds at a constant current of 0.5C, then standing for 10 minutes; discharging for 30 minutes at a constant current of 1.0C, then standing for 30 seconds, and charging for 1 minute at a constant current of 0.5C, then standing for 10 minutes; discharging for 30 seconds at a constant current of 2.0C, then standing for 30 seconds, and charging for 2 minutes at a constant current of 0.5C, then standing for 10 minutes; discharging for 30 seconds at a constant current of 3.0C, then standing for 30 seconds, and charging for 2 minutes at a constant current of 0.5C, then standing for 10 minutes.
The average voltage reduction value of 30 seconds at each C-ratio is a dc voltage value.
A portion of the DC-IR increase calculated from the measured initial DC-IR and the measured DC-IR after high temperature storage is shown in table 6 below. The DC-IR increase is represented by the following equation 6:
equation 6
The increase of the internal resistance of the direct current [% ] = [ internal resistance of the direct current after high-temperature storage/initial internal resistance of the direct current ] x100
TABLE 6
DC-IR increase [%] DC-IR increase [%]
Example 3-1 113 125
Comparative example 1-1 122 137
As shown in table 6, the lithium battery of example 3-1 including the organic electrolyte solution according to the embodiment of the present disclosure showed a decrease in DC-IR increase after high-temperature storage, compared to the lithium battery of comparative example 1-1 not including the organic electrolyte solution.
Lithium battery production (examples G1 to G9, reference examples G1 to G4, and comparative examples G1 and G2)
Example G1: CNT 50 μm 0.5wt% + SEI-1316 1wt%
Manufacture of anode
98wt% of artificial graphite (BSG-L manufactured by Tianjin BTR New Energy Technology co., ltd.) 1.0wt% of SBR (manufactured by ZEON) as a binder and 1.0wt% of CMC (manufactured by NIPPON a & L) were mixed together, the mixture was added to distilled water, and the resulting solution was stirred using a mechanical stirrer for 60 minutes to prepare an anode active material slurry. The anode active material slurry was coated onto a Cu current collector having a thickness of 10 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 ℃ for 0.5 hours, then further dried in vacuo at 120 ℃ for 4 hours, and roll-pressed, thereby completing the fabrication of an anode plate.
Cathode fabrication
96.95wt% of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 0.5wt% of Carbon Nanotube (CNT) having an average length of 50 μm, 0.5wt% of powdered artificial graphite (SFG 6 manufactured by Timcal), 0.7wt% of carbon black (Ketjen black manufactured by ECP), 0.25wt% of modified acrylonitrile rubber (BM-720H manufactured by Zeon corporation), 0.9wt% of PVDF (S6020 manufactured by Solvay) and 0.2wt% of PVDF (S5130 manufactured by Solvay) were mixed together, and the mixture was added to N-methyl-2-pyrrolidone as a solvent and the resulting solution was stirred with a mechanical stirrer for 30 minutes to prepare a cathode active material slurry. The cathode active material slurry was coated on an Al current collector having a thickness of 20 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 ℃ for 0.5 hours, then further dried in vacuum at 120 ℃ for 4 hours, and rolled, thereby completing the fabrication of a cathode plate.
The manufacture of a lithium battery was completed using a polyethylene separator having a thickness of 14 μm and a cathode side coated with ceramic and an organic electrolyte solution prepared according to example 1.
Example G2: CNT 50 μm 1wt% + SEI-1316 1wt%
Except that 96.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 As cathode active materialA lithium battery was fabricated in the same manner as in example G1, except that 1wt% of CNTs having an average length of 50 μm was used as a carbonaceous nanostructure.
Example G3: CNT 50 μm 2wt% + SEI-1316 1wt%
Except that 95.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example G1, except that 2wt% of CNTs having an average length of 50 μm were used as a cathode active material and as a carbonaceous nanostructure.
Example G4: CNT 50 μm 3wt% + SEI-1316 1wt%
Except that 94.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example G1, except that 3wt% of CNT having an average length of 50 μm was used as a cathode active material and as a carbonaceous nanostructure.
Example G5: CNT 50 μm 1wt% + SEI-1316.5 wt%
Except that 96.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 As a cathode active material, a lithium battery was fabricated in the same manner as in example G1, except that 1.0wt% of CNT having an average length of 50 μm was used as a carbonaceous nanostructure and the organic electrolyte solution prepared according to example 3 was used instead of the organic electrolyte solution of example 1.
Example G6: CNT 50 μm 1wt% + SEI-1316 2wt%
Except that 96.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 As a cathode active material, a lithium battery was fabricated in the same manner as in example G1, except that 1.0wt% of CNT having an average length of 50 μm was used as a carbonaceous nanostructure and the organic electrolyte solution prepared according to example 8 was used instead of the organic electrolyte solution of example 1.
EXAMPLE G7 CNT 50 μm 1wt% + SEI-1316 3wt%
Except that 96.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 As a cathode active material, a lithium battery was fabricated in the same manner as in example G1, except that 1.0wt% of CNT having an average length of 50 μm was used as a carbonaceous nanostructure and the organic electrolyte solution prepared according to example 9 was used instead of the organic electrolyte solution of example 1.
Example G8: CNT 5 μm 1wt% + SEI-1316 1wt%
Except that 96.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example G1, except that 1wt% of CNT having an average length of 5 μm was used as a cathode active material, as a carbonaceous nanostructure.
Example G9: CNT 100 μm 1wt% + SEI-1316 1wt%
Except that 96.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example G1, except that 1wt% of CNTs having an average length of 100 μm were used as a cathode active material, as a carbonaceous nanostructure.
Reference example G1: CNT 50 μm 4wt% + SEI-1316 1wt%
Except for 93.45wt% Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example G1, except that 4wt% of CNTs having an average length of 50 μm were used as a cathode active material, as well as a carbonaceous nanostructure.
Reference example G2: CNT 200 μm 1wt% + SEI-1316 1wt%
Except that 96.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example G1, except that 1wt% of CNTs having an average length of 200 μm were used as a cathode active material, as a carbonaceous nanostructure.
Reference example G3: CNT 50 μm 1wt% + SEI-1316 4wt%
Except that 96.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 As a cathode active material, a lithium battery was fabricated in the same manner as in example G1, except that 1wt% of CNT having an average length of 50 μm was used as a carbonaceous nanostructure and the organic electrolyte solution prepared according to example 9a was used instead of the organic electrolyte solution of example 1.
Reference example G4: CNT 50 μm 0.5wt% + SEI-1316 1wt% + NCM111
Except for using LiNi 1/3 Co 1/3 Mn 1/3 O 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example G1, except that a cathode active material was used.
Comparative example G1: CNT 50 μm 1wt% + SEI-1316 wt%
Except that 96.45wt% of Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example G1, except that 1wt% of CNTs having an average length of 50 μm was used as a carbonaceous nanostructure as a cathode active material, and an organic electrolyte solution prepared according to comparative example 1 was used instead of the organic electrolyte solution of example 1.
Comparative example G2: CNT 50 μm 0wt% + SEI-1316 1wt%
Except that 97.45wt% Li was used 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example G1, except that the carbonaceous nanostructure was not added as a cathode active material.
Evaluation example G1: evaluation of charging and discharging characteristics at 4.25V and high temperature (45 ℃ C.)
The charge and discharge characteristics of lithium batteries manufactured according to examples G1 to G9, reference examples G1 to G4, and comparative examples G1 and G2 were evaluated at high temperatures using the same method as that used in evaluation example 2, except that the number of charge and discharge cycles was changed to 300 cycles.
A part of the charge and discharge experimental results are shown in the following table G1. The capacity retention rate of the 300 th cycle is defined using the following equation 7:
equation 7
Capacity retention = [ discharge capacity at 300 th cycle/discharge capacity at 1 st cycle ] ×100
Table G1
As shown in table G1, the lithium batteries of examples G1 to G9 including the additive and the CNT according to the embodiments of the present disclosure exhibited enhanced lifetime characteristics at high temperature, as compared to the lithium battery of comparative example G1 including no additive or comparative example G2 including no CNT.
Further, the lithium batteries of examples G1 to G9 including CNTs having a length within a certain range exhibited enhanced lifetime characteristics at high temperatures as compared with the lithium battery of reference example G2 including CNTs having a length outside the certain range.
Evaluation example G2: DC-IR evaluation after high temperature (60 ℃ C.) storage
DC-IR of the lithium batteries of examples G1 to G9, reference examples G1 to G3, and comparative examples G1 and G2 after high-temperature storage was measured using the same method as that used in evaluation example 6.
A portion of the DC-IR increase calculated from the measured initial DC-IR and the measured DC-IR after high temperature storage is shown in table G2 below. The DC-IR increase is represented by the following equation 6:
equation 6
The increase of the internal resistance of the direct current [% ] = [ the internal resistance of the direct current after high-temperature storage/the initial internal resistance of the direct current ] ×100
Table G2
As shown in table G2, the lithium batteries of examples G1 to G9 including the additive and the CNT according to the embodiment of the present disclosure showed lower DC-IR increase than the lithium batteries of comparative example G1 including no additive and comparative example G2 including no CNT.
Evaluation example G3: evaluation of impregnation amount
The cathodes manufactured according to examples G1 to G9, reference examples G1 to G3, and comparative examples G1 and G2 were subjected to impregnation amount measurement using the following methods.
By mixing 1.15M LiPF 6 An electrolyte solution was prepared by dissolving in a mixed solvent of ethylene carbonate/methylethyl carbonate/dimethyl carbonate (EC/EMC/DMC) in a volume ratio of 2:4:4 and adding 1wt% of Vinylene Carbonate (VC) to the resulting solution. Each cathode plate was cut into a size of 3cm x 6cm and then immersed in the prepared electrolyte solution to quantitatively measure the amount of electrolyte solution used to impregnate the cathode plate for 300 seconds. After immersing each cathode plate in the electrolyte solution for 300 seconds, the immersion amount was measured using an atlasion Sigma device.
The measured impregnation amounts are shown in the following table G3.
Table G3
As shown in table G3, the lithium batteries of examples G1 to G4 including the additive and the CNT according to the embodiment of the present disclosure exhibited increased impregnation amounts as compared to the lithium batteries of comparative example G1 including no additive and comparative example G2 including no CNT.
Furthermore, the lithium batteries of examples G1 to G9 including CNTs having a length within a certain range exhibited increased impregnation amounts as compared to the lithium battery of reference example G2 including CNTs having a length outside the certain range.
Since the lithium batteries of examples G1 to G9 have enhanced impregnation characteristics, the contact area between the electrode and the electrolyte solution increases. Therefore, the reversibility of the electrode reaction is enhanced, and thus the lithium battery has reduced internal resistance, resulting in an enhancement of the cycle characteristics of the lithium battery.
By way of summary and review, aqueous electrolyte solutions that are highly reactive to lithium may not be suitable for use in lithium batteries when such batteries are operated at high operating voltages. Lithium batteries typically use organic electrolyte solutions. The organic electrolyte solution is prepared by dissolving a lithium salt in an organic solvent. An organic solvent having stability at a high voltage, high ionic conductivity, high dielectric constant and low viscosity may be used.
When a lithium battery uses a general organic electrolyte solution including a carbonate-based polar nonaqueous solvent, irreversible reaction of excessive use of charges due to side reactions between an anode/cathode and the organic electrolyte solution may occur during initial charge. Due to such irreversible reaction, a passivation layer, such as a Solid Electrolyte Interface (SEI) layer, may be formed on the surface of the anode. In addition, a protective layer is formed on the surface of the cathode.
In this regard, the SEI layer and/or the protective layer formed using the existing organic electrolyte solution may be easily degraded. For example, such an SEI layer and/or protective layer may exhibit reduced stability at high temperatures.
Accordingly, an organic electrolyte solution capable of forming an SEI layer and/or a protective layer having improved high temperature stability is desired.
Various embodiments of the present application provide a lithium battery including: a carbonaceous nanostructure; and an organic electrolyte solution comprising a novel bicyclic sulfate-based additive. The lithium battery according to the embodiment exhibits enhanced high temperature characteristics and enhanced life characteristics.
Exemplary embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purpose of limitation. In some cases, it will be apparent to one of ordinary skill in the art at the time of filing the present disclosure that the features, characteristics, and/or elements described in connection with the particular embodiments may be used alone or in combination with the features, characteristics, and/or elements described in connection with other embodiments unless explicitly stated otherwise. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope thereof as set forth in the appended claims.

Claims (20)

1. A lithium battery, comprising:
a cathode including a cathode active material;
an anode comprising an anode active material; and
an organic electrolyte solution between the cathode and the anode,
Wherein the cathode comprises carbonaceous nanostructures, wherein the amount of carbonaceous nanostructures is from 0.5wt% to 3wt%, based on the total weight of the cathode mixture, and wherein the carbonaceous nanostructures have an average length of 1 μιη and less than 200 μιη, and
the organic electrolyte solution includes a first lithium salt, an organic solvent, and a bicyclic sulfate-based compound represented by the following formula 1:
< 1>
Wherein in formula 1, A 1 、A 2 、A 3 And A 4 Each independently is a covalent bond, substituted or unsubstituted C 1 -C 5 Alkylene, carbonyl or sulfinyl, wherein A 1 And A 2 Not all are covalent bonds, and A 3 And A 4 Not all of them are covalent bonds and,
wherein the amount of the dicyclo sulfate-based compound is 0.4wt% to 3wt%, based on the total weight of the organic electrolyte solution.
2. The lithium battery of claim 1, wherein a 1 、A 2 、A 3 And A 4 At least one of which is unsubstituted or substituted C 1 -C 5 Alkylene group, wherein the substituted C 1 -C 5 The substituent of the alkylene group is at least one selected from the following: halogen substituted or unsubstituted C 1 -C 20 Substituted or unsubstituted by alkyl, halogenSubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen-substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl or a polar functional group having at least one heteroatom.
3. The lithium battery of claim 1, wherein a 1 、A 2 、A 3 And A 4 At least one of which is unsubstituted or substituted C 1 -C 5 Alkylene group, wherein the substituted C 1 -C 5 The substituent of the alkylene group is halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
4. The lithium battery of claim 2, wherein the substituted C 1 -C 5 The substituent of the alkylene group includes the polar functional group having at least one heteroatom, wherein the polar functional group is at least one selected from the group consisting of: -F, -Cl, -Br, -I, -C (=o) OR 16 、-OR 16 、-OC(＝O)OR 16 、-R 15 OC(＝O)OR 16 、-C(＝O)R 16 、-R 15 C(＝O)R 16 、-OC(＝O)R 16 、-R 15 OC(＝O)R 16 、-C(＝O)-O-C(＝O)R 16 、-R 15 C(＝O)-O-C(＝O)R 16 、-SR 16 、-R 15 SR 16 、-SSR 16 、-R 15 SSR 16 、-S(＝O)R 16 、-R 15 S(＝O)R 16 、-R 15 C(＝S)R 16 、-R 15 C(＝S)SR 16 、-R 15 SO 3 R 16 、-SO 3 R 16 、-NNC(＝S)R 16 、-R 15 NNC(＝S)R 16 、-R 15 N＝C＝S、-NCO、-R 15 -NCO、-NO 2 、-R 15 NO 2 、-R 15 SO 2 R 16 、-SO 2 R 16 、
Wherein, in the above formula, R 11 And R is 15 Each independently is halogen substituted or unsubstituted C 1 -C 20 Alkylene, halogen substituted or unsubstituted C 2 -C 20 Alkenylene, halogen substituted or unsubstituted C 2 -C 20 Alkynylene, halogen substituted or unsubstituted C 3 -C 12 Cycloalkylene, halogen substituted or unsubstituted C 6 -C 40 Arylene, halogen substituted or unsubstituted C 2 -C 40 Heteroarylene, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl or halogen substituted or unsubstituted C 7 -C 15 An aralkylene group; and is also provided with
R 12 、R 13 、R 14 And R is 16 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 12 Cycloalkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl, halogen substituted or unsubstituted C 7 -C 15 Trialkylsilyl or halogen substituted or unsubstituted C 7 -C 15 Aralkyl groups.
5. The lithium battery of claim 1, wherein the bicyclic sulfate-based compound is represented by formula 2 or formula 3:
wherein in formula 2 and formula 3, B 1 、B 2 、B 3 、B 4 、D 1 And D 2 Each independently is-C (E) 1 )(E 2 ) -carbonyl or sulfinyl; and is also provided with
E 1 And E is 2 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
6. The lithium battery of claim 5, wherein E 1 And E is 2 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 10 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
7. The lithium battery of claim 5, wherein E 1 And E is 2 Each independently is at least one selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl, and pyridyl.
8. The lithium battery of claim 1, wherein the bicyclic sulfate-based compound is represented by formula 4 or formula 5:
wherein in formula 4 and formula 5, R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
9. The lithium battery of claim 8, wherein R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 Each independently is hydrogen, F, cl, br, I, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl, or pyridinyl.
10. The lithium battery of claim 1, wherein the bicyclic sulfate-based compound is represented by one of the following formulas 6 to 17:
11. The lithium battery of claim 1, wherein the first lithium salt in the organic electrolyte solution comprises at least one selected from the group consisting of: liPF (LiPF) 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiClO 4 、LiCF 3 SO 3 、Li(CF 3 SO 2 ) 2 N、LiC 4 F 9 SO 3 、LiAlO 2 、LiAlCl 4 LiCl, liI and LiN (C) x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) Wherein x is more than or equal to 2 and less than or equal to 20, and y is more than or equal to 2 and less than or equal to 20.
12. The lithium battery of claim 1, wherein the organic electrolyte solution further comprises a cyclic carbonate compound, wherein the cyclic carbonate compound is selected from the group consisting of vinylene carbonate, vinylene carbonate substituted with at least one substituent selected from the group consisting of halogen, cyano and nitro, fluoroethylene carbonate, and fluoroethylene carbonate substituted with at least one substituent selected from the group consisting of halogen, cyano and nitro.
13. The lithium battery of claim 12, wherein the amount of the cyclic carbonate compound is 0.01wt% to 5wt%, based on the total weight of the organic electrolyte solution.
14. The lithium battery of claim 1, wherein the organic electrolyte solution further comprises a second lithium salt represented by one of the following formulas 18 to 25:
15. The lithium battery of claim 14, wherein the amount of the second lithium salt is 0.1wt% to 5wt%, based on the total weight of the organic electrolyte solution.
16. The lithium battery of claim 1, wherein the carbonaceous nanostructure comprises at least one selected from the group consisting of one-dimensional carbonaceous nanostructure and two-dimensional carbonaceous nanostructure.
17. The lithium battery of claim 1, wherein the carbonaceous nanostructure comprises at least one selected from the group consisting of carbon nanotubes, carbon nanofibers, graphene nanoplatelets, hollow carbon, porous carbon, and mesoporous carbon.
18. The lithium battery of claim 1, wherein the cathode comprises a nickel-containing layered lithium transition metal oxide.
19. The lithium battery of claim 18, wherein the nickel content in the lithium transition metal oxide is 60mol% or more relative to the total moles of transition metal.
20. The lithium battery of claim 18, wherein the lithium transition metal oxide is a compound represented by the following formula 27 or formula 28:
< 27>
LiNi x Co y Mn z O 2
< 28>
LiNi x Co y Al z O 2
Wherein in the formulas 27 and 28, 0.6.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.2, 0< z.ltoreq.0.2, and x+y+z=1.
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