CN110931857A - Lithium battery - Google Patents

Lithium battery Download PDF

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CN110931857A
CN110931857A CN201910360743.2A CN201910360743A CN110931857A CN 110931857 A CN110931857 A CN 110931857A CN 201910360743 A CN201910360743 A CN 201910360743A CN 110931857 A CN110931857 A CN 110931857A
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halogen substituted
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electrolyte solution
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孙美暎
金暻洙
金允熙
金载弘
罗哈娜
柳洙烈
禹明希
李承泰
李河林
郑明焕
车始英
崔善珠
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Samsung SDI Co Ltd
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Priority claimed from US16/135,301 external-priority patent/US11637322B2/en
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Priority to CN202410134872.0A priority Critical patent/CN117747951A/en
Priority to KR1020190114966A priority patent/KR102510887B1/en
Publication of CN110931857A publication Critical patent/CN110931857A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The 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. The cathode active material includes a nickel-containing layered lithium transition metal oxide. The nickel content in the lithium transition metal oxide is about 60 mol% or more with respect to the total moles of transition metals. The organic electrolyte solution includes a first lithium salt, an organic solvent, and a bicyclic sulfate-based compound represented by the following formula 1:<formula 1>
Figure DDA0002046741150000011
Wherein, in formula 1, A1、A2、A3And A4Each independently a covalent bond, a substituted or unsubstituted C1-C5 alkylene, carbonyl, or sulfinyl group, wherein A is1And A2Are not all covalent bonds, and A3And A4Not all are covalent bonds.

Description

Lithium battery
Cross Reference to Related Applications
The present application claims the benefit of U.S. patent application serial No. 15/422,873 entitled "lithium battery," filed 2018, 9/19/8, U.S. continuation-in-part application No. 16/135,301, the entire contents of which are incorporated herein by reference.
Technical Field
Various embodiments of the present invention 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 an 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: the electrolyte composition includes a cathode including a cathode active material, an anode including an anode active material, and an organic electrolyte solution between the cathode and the anode. The cathode active material includes a nickel-containing layered lithium transition metal oxide. The nickel content in the lithium transition metal oxide is about 60 mol% or more with respect to the total moles of transition metals in the lithium transition metal oxide. The organic electrolyte solution includes a first lithium salt, an organic solvent, and a bicyclic sulfate-based compound represented by the following formula 1:
< formula 1>
Figure BDA0002046741130000011
Wherein, in formula 1, A1、A2、A3And A4Each independently being a covalent bond, substituted or unsubstituted C1-C5Alkylene, carbonyl or sulfinyl, in which A1And A2Are not all covalent bonds, and A3And A4Not all are covalent bonds.
A1、A2、A3And A4At least one of which is unsubstituted or substituted C1-C5Alkylene, wherein C is substituted1-C5The substituent of the alkylene group is at least one selected from the group consisting of: halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen-substituted or unsubstituted C3-C20Heterocyclic radical, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl or a polar functional group having at least one heteroatom.
A1、A2、A3And A4At least one of which is unsubstituted or substituted C1-C5Alkylene oxideGroup, wherein C is substituted1-C5The substituent of the alkylene group is halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
The substituent of the substituted C1-C5 alkylene group may include a 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) OR16、-OR16、-OC(＝O)OR16、-R15OC(＝O)OR16、-C(＝O)R16、-R15C(＝O)R16、-OC(＝O)R16、-R15OC(＝O)R16、-C(＝O)-O-C(＝O)R16、-R15C(＝O)-O-C(＝O)R16、-SR16、-R15SR16、-SSR16、-R15SSR16、-S(＝O)R16、-R15S(＝O)R16、-R15C(＝S)R16、-R15C(＝S)SR16、-R15SO3R16、-SO3R16、-NNC(＝S)R16、-R15NNC(＝S)R16、-R15N＝C＝S、-NCO、-R15-NCO、-NO2、-R15NO2、-R15SO2R16、-SO2R16、
Figure BDA0002046741130000021
Figure BDA0002046741130000022
Figure BDA0002046741130000031
Figure BDA0002046741130000032
Wherein, in the above formula, R11And R15Each independently halogen substituted or unsubstituted C1-C20Alkylene radicalHalogen substituted or unsubstituted C2-C20Alkenylene, halogen substituted or unsubstituted C2-C20Alkynylene, halogen substituted or unsubstituted C3-C12Cycloalkylene, halogen substituted or unsubstituted C6-C40Arylene, halogen substituted or unsubstituted C2-C40Heteroarylene, halogen substituted or unsubstituted C7-C15Alkylarylene or halogen substituted or unsubstituted C7-C15An aralkylene group; and R is12、R13、R14And R16Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C12Cycloalkyl, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl, halogen substituted or unsubstituted C7-C15Alkylaryl, halogen substituted or unsubstituted C7-C15Trialkylsilyl or halogen substituted or unsubstituted C7-C15Aralkyl, and
Figure BDA0002046741130000033
representing the binding site to the adjacent atom.
The bicyclic sulfate-based compound may be represented by formula 2 or 3:
Figure BDA0002046741130000034
wherein, in formulae 2 and 3, B1、B2、B3、B4、D1And D2Each independently is-C (E)1)(E2) -, carbonyl or sulfinyl; and E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen substituted or unsubstituted C3-C20Heterocyclic radical, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C10Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
E1And E2May each independently be hydrogen, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
The bicyclic sulfate-based compound may be represented by formula 4 or formula 5:
Figure BDA0002046741130000035
Figure BDA0002046741130000041
wherein, in formula 4 and formula 5, R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Can each independently be hydrogen, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, tert-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:
Figure BDA0002046741130000042
Figure BDA0002046741130000051
the amount of the bicyclic sulfate-based compound may be about 0.4 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution.
The amount of the bicyclic sulfate-based compound may be about 0.4 wt% to about 3 wt%, 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: LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiCF3SO3、Li(CF3SO2)2N、LiC4F9SO3、LiAlO2、LiAlCl4、LiN(CxF2x+1SO2)(CyF2y+1SO2) (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 organic electrolyte solution may further comprise a cyclic carbonate compound, wherein the cyclic carbonate compound is selected from Vinylene Carbonate (VC) selected from halogen, cyano (-CN), and nitro (-NO)2) VC substituted with at least one substituent in (a), Vinyl Ethylene Carbonate (VEC), is selected from halogen, -CN and-NO2VEC substituted with at least one substituent selected from the group consisting of halogen, -CN and-NO, fluoroethylene carbonate (FEC)2FEC substituted with at least one substituent of (a).
The amount of the cyclic carbonate compound may be about 0.01 wt% to about 5 wt% based on the total weight of the organic electrolyte solution.
The organic electrolyte solution may further include a second lithium salt, which is different from the first lithium salt and is represented by one of the following formulae 18 to 25:
Figure BDA0002046741130000052
Figure BDA0002046741130000061
the amount of the second lithium salt may be about 0.1 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution.
The lithium transition metal oxide may be represented by the following formula 26:
< formula 26>
LiaNixCoyMzO2-bAb
Wherein, in formula 26, 1.0. ltoreq. a.ltoreq.1.2, 0. ltoreq. b.ltoreq.0.2, 0.6. ltoreq. x <1, 0< y. ltoreq.0.2, 0< z. ltoreq.0.2, and x + y + z 1. M may be at least one selected from the group consisting of: 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). A may be fluorine (F), sulfur (S), chlorine (Cl), bromine (Br), or a combination thereof.
The lithium transition metal oxide may be a compound represented by formula 27 or formula 28 below:
< formula 27>
LiNixCoyMnzO2
< formula 28>
LiNixCoyAlzO2
Wherein, in formulae 27 and 28, 0.6. ltoreq. x.ltoreq.0.95, 0< y.ltoreq.0.2, 0< z.ltoreq.0.2, and x + y + z is 1.
The lithium battery may have a high voltage of about 3.8V or more.
Drawings
Various features will become apparent to those skilled in the art from the following detailed description of exemplary embodiments, which proceeds 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 at high temperatures of lithium batteries of examples 1-1 and 2-1 and comparative example 1-1;
FIG. 4 shows graphs showing capacity retention rates at high temperatures of lithium batteries of examples 1-1 and 2-1 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
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 exemplary embodiments to those skilled in the art.
A lithium battery according to an embodiment includes: the electrolyte includes a cathode containing a cathode active material, an anode containing an anode active material, and an organic electrolyte solution disposed between the cathode and the anode. The cathode active material may include a nickel-containing layered lithium transition metal oxide. The nickel content in the lithium transition metal oxide may be about 60 mol% or more with respect to the total moles of transition metals. The organic electrolyte solution may include a first lithium salt; an organic solvent; and a bicyclic sulfate-based compound represented by the following formula 1:
< formula 1>
Figure BDA0002046741130000071
Wherein, in formula 1, A1、A2、A3And A4Each independently being a covalent bond, substituted or unsubstituted C1-C5Alkylene, carbonyl or sulfinyl, in which A1And A2Are not all covalent bonds, and A3And A4Not all are covalent bonds.
An organic electrolyte solution including a bicyclic sulfate-based compound as an additive for a lithium battery may enhance battery performance, such as high temperature characteristics, life characteristics, and the like.
In addition, when the cathode active material in the cathode includes a nickel-containing layered lithium transition metal oxide, and the Ni content in the lithium transition metal oxide is about 60 mol% or more with respect to the total moles of transition metals, the lithium battery may exhibit further enhanced life characteristics and further enhanced high temperature stability.
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 the lithium battery by adding the bicyclic sulfate-based compound to the electrolyte solution will now be described in further detail.
When the bicyclo sulfate-based compound is included in the electrolyte solution, the sulfate group of the bicyclo sulfate-based compound may be reduced by itself by accepting an electron from the surface of the anode during charging, or may react with a previously reduced polar solvent molecule, thereby affecting the characteristics of the SEI layer formed on the surface of the anode. For example, bicyclic sulfate-based compounds containing a sulfate group may accept electrons more readily from the anode than polar solvents. For example, bicyclic sulfate-based compounds may be reduced at a lower voltage than is required for polar solvent reduction before the polar solvent is reduced.
For example, bicyclic sulfate-based compounds include sulfate groups and thus may be more readily reduced and/or decomposed into radicals and/or ions during charging. As a result, radicals and/or ions may be combined with lithium ions to form an appropriate SEI layer on the anode, thereby preventing formation of a product 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 having improved stability formed by such bonding and/or adsorption may be more durable even after long-term charge and discharge, as compared to an SEI layer formed only of an organic solvent. The durable modified SEI layer may instead more effectively prevent co-intercalation of solvated lithium ions by the organic solvent during lithium ion intercalation into the electrode. Accordingly, the modified SEI layer can more effectively prevent direct contact between the organic solvent and the anode to further improve the 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, the bicyclic sulfate-based compound may coordinate on the surface of the cathode due to the sulfate group, thereby affecting the characteristics of the protective layer formed on the surface of the cathode. 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 having improved stability, which is more durable than a protective layer formed only of an organic solvent even after a long-time charge and discharge. In addition, the durable modified protective layer may more effectively prevent co-intercalation of solvated lithium ions by the organic solvent during intercalation of lithium ions into the electrode. Therefore, the modified protective layer may 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.
In addition, the bicyclic sulfate-based compound has a structure in which a plurality of rings are connected in a spiro form, and thus has a relatively larger molecular weight than a general sulfate-based compound, and thus, it may be thermally stable.
For example, the bicyclic sulfate-based compound may form an SEI layer at a protective layer of an anode surface or a cathode surface, and it may exhibit enhanced life characteristics of a lithium battery manufactured at high temperature due to improved thermal stability.
In the bicyclic sulfate-based compound of the above formula 1 contained in an organic electrolyte solution, A1、A2、A3And A4At least one of which may be unsubstituted or substituted C1-C5Alkylene, and substituted C1-C5The substituent of the alkylene group may be a halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen substituted or unsubstituted C3-C20Heterocyclic radical, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl or a polar functional group having at least one heteroatom.
For example, A1、A2、A3And A4At least one of which may be unsubstituted or substituted C1-C5Alkylene, and substituted C1-C5The substituent for the alkylene group may be halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl. For example, the substituent of a substituted C1-C5 alkylene group can be a suitable substituent for alkylene groups used in the art.
In some embodiments, in the bicyclic sulfate-based compound of formula 1 above, substituted C is1-C5The substituent of the alkylene group may be a polar functional group having a hetero atom. The hetero atom of the polar functional group may be at least one selected from halogen, oxygen, nitrogen, phosphorus, sulfur, silicon, and boron.
For example, polar functional groups having hetero atomsThe functional group may be at least one selected from the group consisting of: -F, -Cl, -Br, -I, -C (═ O) OR16、-OR16、-OC(＝O)OR16、-R15OC(＝O)OR16、-C(＝O)R16、-R15C(＝O)R16、-OC(＝O)R16、-R15OC(＝O)R16、-C(＝O)-O-C(＝O)R16、-R15C(＝O)-O-C(＝O)R16、-SR16、-R15SR16、-SSR16、-R15SSR16、-S(＝O)R16、-R15S(＝O)R16、-R15C(＝S)R16、-R15C(＝S)SR16、-R15SO3R16、-SO3R16、-NNC(＝S)R16、-R15NNC(＝S)R16、-R15N＝C＝S、-NCO、-R15-NCO、-NO2、-R15NO2、-R15SO2R16、-SO2R16、
Figure BDA0002046741130000091
Figure BDA0002046741130000092
Figure BDA0002046741130000101
In the above formula, R11And R15Each independently may be halogen substituted or unsubstituted C1-C20Alkylene, halogen substituted or unsubstituted C2-C20Alkenylene, halogen substituted or unsubstituted C2-C20Alkynylene, halogen substituted or unsubstituted C3-C12Cycloalkylene, halogen substituted or unsubstituted C6-C40Arylene, halogen substituted or unsubstituted C2-C40Heteroarylene, halogen substituted or unsubstituted C7-C15Alkylarylene or halogen substituted or unsubstituted C7-C15An aralkylene group. R12、R13、R14And R16Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C12Cycloalkyl, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl, halogen substituted or unsubstituted C7-C15Alkylaryl, halogen substituted or unsubstituted C7-C15Trialkylsilyl or halogen substituted or unsubstituted C7-C15Aralkyl, and
Figure BDA0002046741130000102
representing the binding site to the adjacent atom.
For example, in the polar functional group having a hetero atom, the halogen substituent of the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, heteroaryl group, alkylaryl group, trialkylsilyl group or arylalkyl group may be fluorine (F).
For example, the bicyclic sulfate-based compound contained in the organic electrolyte solution may be represented by formula 2 or 3:
Figure BDA0002046741130000103
wherein, in formulae 2 and 3, B1、B2、B3、B4、D1And D2May each independently be-C (E)1)(E2) -, carbonyl or sulfinyl. E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen substituted or unsubstituted C3-C20Heterocyclic ringsAlkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
E.g. E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C10Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
E.g. E1And E2May each independently be hydrogen, F, chlorine (Cl), bromine (Br), iodine (I), methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
E.g. E1And E2Each independently can be hydrogen, F, methyl, ethyl, trifluoromethyl, tetrafluoroethyl, or phenyl.
For example, bicyclic sulfate-based compounds may be represented by formula 4 or 5:
Figure BDA0002046741130000111
wherein, in formula 4 and formula 5, R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
For example, in the above formulas 4 and 5, R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Can be each independently hydrogen, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, benzenePhenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
For example, in the above formulas 4 and 5, R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently can be hydrogen, F, methyl, ethyl, propyl, trifluoromethyl, tetrafluoroethyl, or phenyl.
For example, the bicyclic sulfate-based compound may be represented by one of the following formulas 6 to 17:
Figure BDA0002046741130000112
Figure BDA0002046741130000121
as used herein, the expression "Ca-Cb"a and b" represent the number of carbon atoms of the specific functional group. For example, the functional group may include a to b carbon atoms. For example, the expression "C1-C4Alkyl "denotes an alkyl group having 1 to 4 carbon atoms, i.e. CH3-、CH3CH2-、CH3CH2CH2-、(CH3)2CH-、CH3CH2CH2CH2-、CH3CH2CH(CH3) -and (CH)3)3C-。
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, a substituent designated as alkyl requiring two binding sites may be a divalent group, such as-CH2-、-CH2CH2-、-CH2CH(CH3)CH2-and the like. The term "alkylene" as used herein means that the group is a divalent group.
The terms "alkyl" and "alkylene" as used herein refer to branched or unbranched aliphatic hydrocarbonsAnd (4) a base. In one embodiment, an alkyl group may be substituted or unsubstituted. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-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. E.g. C1-C6The alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, 3-pentyl, hexyl, and the like.
The term "cycloalkyl" as used herein refers to a fully saturated carbocyclic ring or ring system. For example, cycloalkyl groups can 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 ethenyl, 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, the alkenyl group 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, the alkynyl group may have 2 to 40 carbon atoms.
The term "aromatic" as used herein refers to rings or ring systems having conjugated pi-electron systems, and may refer to carbocyclic aromatic groups (e.g., phenyl) and heterocyclic aromatic groups (e.g., pyridine). In this regard, the aromatic ring system may comprise a single ring or fused multiple rings (i.e., rings that share adjacent pairs of atoms) as a whole.
The term "aryl" as used herein refers to an aromatic ring or ring system having only carbon atoms in its backbone (i.e., a ring fused by at least two rings sharing two adjacent carbon atoms). When the aryl group 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 fused ring systems, 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 connected by an alkylene group in the form of a substituent, e.g., C7-C14An aralkyl group. Examples of aralkyl or alkylaryl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and naphthylalkyl. In one embodiment, alkylene may be lower alkylene (i.e., C)1-C4Alkylene).
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 can 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 stabilizing element belonging to group 17 of the periodic table of elements, such as fluorine, chlorine, bromine or iodine. For example, the halogen may be fluorine and/or chlorine.
In the present specification, a substituent may be obtained by substituting at least one hydrogen atom in an unsubstituted parent group with another atom or functional group. Unless otherwise indicated, the term "substituted" means that the functional groups listed above are substituted with at least one substituent selected from the group consisting of: c1-C40Alkyl radical, C2-C40Alkenyl radical, C3-C40Cycloalkyl radical, C3-C40Cycloalkenyl radical and C7-C40And (4) an aryl group. 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 0.4 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution. For example, 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 0.4 wt% to about 3 wt% 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 range from about 0.6 wt% to about 3 wt%, 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 about 0.7 wt% to about 3 wt% 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 about 0.4 wt% to about 2.5 wt%, 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 about 0.4 wt% to about 2 wt% 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 about 0.4 wt% to about 1.5 wt% based on the total weight of the organic electrolyte solution. When the amount of the bicyclic sulfate-based compound of formula 1 is within the above range, further enhanced battery characteristics may be obtained.
The first lithium salt contained in the organic electrolyte solution may include at least one selected from the group consisting of: LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiCF3SO3、Li(CF3SO2)2N、LiC4F9SO3、LiAlO2、LiAlCl4、LiN(CxF2x+1SO2)(CyF2y+1SO2) (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 necessary. When the concentration of the first lithium salt is within the above range, a battery having further enhanced characteristics may be obtained.
The organic solvent contained in the organic electrolyte solution may be a low boiling point solvent. The term "low boiling solvent" refers to 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), Ethyl Methyl Carbonate (EMC), propyl methyl carbonate, propyl ethyl 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 a suitable solvent having a low boiling point available in the art.
The organic electrolyte solution may further include other additives in addition to the bicyclic sulfate-based compound. By further containing other additives, a lithium battery having further enhanced performance can be obtained.
The additive further contained in the organic electrolyte solution may include a cyclic carbonate compound, a second lithium salt, and the like.
For example, the organic electrolyte solution may further include a cyclic carbonate compound as an additive. The cyclic carbonate compound used as an additive may be selected from Vinylene Carbonate (VC) selected from halogen, cyano (-CN) and nitro (-NO)2) VC substituted with at least one substituent in (a), Vinyl Ethylene Carbonate (VEC), is selected from halogen, -CN and-NO2VEC substituted with at least one substituent of (a); fluoroethylene carbonate (FEC), and selected from halogen, -CN and-NO2FEC substituted with at least one substituent of (a). When the organic electrolyte solution further includes a cyclic carbonate compound as an additive, the lithium battery including the organic electrolyte solution may have further enhanced charge and discharge characteristics.
The amount of the cyclic carbonate compound in the organic electrolyte solution may be, for example, about 0.01 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution. The amount of the cyclic carbonate compound may be appropriately adjusted as necessary. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be about 0.1 wt% to about 5 wt% based on the total weight of the organic electrolyte solution. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be about 0.1 wt% to about 4 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be about 0.1 wt% to about 3 wt% based on the total weight of the organic electrolyte solution. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be about 0.1 wt% to about 2 wt% based on the total weight of the organic electrolyte solution. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be about 0.2 wt% to about 2 wt% based on the total weight of the organic electrolyte solution. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be about 0.2 wt% to about 1.5 wt%, 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 may be obtained.
For example, the organic electrolyte solution may further include a second lithium salt as an additive. The second lithium salt is distinct (i.e., different) from the first lithium salt. The anion of the second lithium salt may be oxalate or PO2F2 -、N(SO2F)2 -And the like. For example, the second lithium salt may be a compound represented by one of the following formulae 18 to 25:
Figure BDA0002046741130000151
Figure BDA0002046741130000161
the amount of the second lithium salt in the organic electrolyte solution may be about 0.1 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution. The amount of the second lithium salt may be appropriately adjusted, if necessary. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.1 wt% to about 4.5 wt%, 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 0.1 wt% to about 4 wt%, 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 0.1 wt% to about 3 wt%, 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 0.1 wt% to about 2 wt%, 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 0.2 wt% to about 2 wt%, 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 0.2 wt% to about 1.5 wt%, 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 may be obtained.
The organic electrolyte solution may be in a liquid state or a 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 nickel-containing layered lithium transition metal oxide included in the cathode of the lithium battery may be represented, for example, by the following formula 26:
< formula 26>
LiaNixCoyMzO2-bAb
Wherein, in formula 26, a is not less than 1.0 and not more than 1.2, b is not less than 0 and not more than 0.2, x is not less than 0.6 and not more than 1, y is not less than 0.2 and 0 is not less than 0.2, and x + y + z is 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 ≦ x <1, 0< y ≦ 0.15, 0< z ≦ 0.15, and x + y + z ≦ 1. For example, 0.75 ≦ x <1, 0< y ≦ 0.125, 0< z ≦ 0.125, and x + y + z ≦ 1. For example, 0.8 ≦ x <1, 0< y ≦ 0.1, 0< z ≦ 0.1, and x + y + z ≦ 1. For example, 0.85 ≦ x <1, 0< y ≦ 0.075, 0< z ≦ 0.075, and x + y + z ≦ 1.
The nickel-containing layered lithium transition metal oxide included in the cathode of the lithium battery may be represented by, for example, formula 27 or formula 28:
< formula 27>
LiNixCoyMnzO2
< formula 28>
LiNixCoyAlzO2
Wherein, in formula 27 and formula 28, 0.6. ltoreq. x.ltoreq.0.95, 0< y.ltoreq.0.2, 0< z.ltoreq.0.2, and x + y + z is 1. For example, 0.7 ≦ x ≦ 0.95, 0< y ≦ 0.15, 0< z ≦ 0.15, and x + y + z ≦ 1. For example, 0.75 ≦ x ≦ 0.95, 0< y ≦ 0.125, 0< z ≦ 0.125, and x + y + z ≦ 1. For example, 0.8 ≦ x ≦ 0.95, 0< y ≦ 0.1, 0< z ≦ 0.1, and x + y + z ≦ 1. For example, 0.85 ≦ x ≦ 0.95, 0< y ≦ 0.075, 0< z ≦ 0.075, and x + y + z ≦ 1.
Examples of the lithium battery include a lithium secondary battery (e.g., a lithium ion battery, a lithium ion polymer battery, a lithium sulfur battery, etc.) and a lithium primary battery.
For example, in a lithium battery, the anode may include graphite. For example, lithium batteries may have a high voltage of about 3.80V or higher. For example, lithium batteries may have a high voltage of about 4.0V or higher. For example, lithium batteries may have a high voltage of about 4.35V or higher.
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 may be prepared in which the above-described cathode active material, conductive material, binder, and solvent are mixed. The cathode active material composition may be directly coated on a metal current collector, thereby completing the manufacture of a cathode plate. In some embodiments, 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 manufacture of a cathode plate.
For example, the cathode active material may be a compound represented by any one of the following formulae: liaA1-bB'bD2Wherein 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; liaE1-bB'bO2-cDcWherein a is more than or equal to 0.90 and less than or equal to 1.8, 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; LiE2-bB'bO4-cDcWherein 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; liaNi1-b-cCobB'cDαWherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less 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；LiaNi1-b-cCobB'cO2-αF'αWherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less 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；LiaNi1-b-cCobB'cO2-αF'2Wherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less 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；LiaNi1-b-cMnbB'cDαWherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less 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；LiaNi1-b-cMnbB'cO2-αF'αWherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less 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；LiaNi1-b-cMnbB'cO2-αF'2Wherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less 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；LiaNibEcGdO2Wherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less 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; liaNibCocMndGeO2Wherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less 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; liaNiGbO2Wherein 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; liaCoGbO2Wherein 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; liaMnGbO2Wherein 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; liaMn2GbO4Wherein 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; QO2；QS2；LiQS2；V2O5；LiV2O5；LiI'O2；LiNiVO4；Li(3-f)J2(PO4)3Wherein f is more than or equal to 0 and less than or equal to 2; li(3-f)Fe2(PO4)3Wherein f is more than or equal to 0 and less than or equal to 2; and LiFePO4。
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 further include LiCoO2；LiMnxO2xWherein x is 1 or 2; LiNi1-xMnxO2xWherein 0 is<x<1；LiNi1-x-yCoxMnyO2Wherein 0 is<1-x-y<0.6, 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; LiFePO4And the like.
In addition, the lithium-containing metal oxide for a cathode active material described above 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 the surface thereof may be used. The coating may comprise a coating element compound, such as a coating element oxide, a coating element hydroxide, a coating element oxyhydroxide, a coating element oxycarbonate, or a coating element hydroxycarbonate. The coating element compound may be amorphous or crystalline. The coating element included in the coating layer may be selected from the group consisting of 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 a mixture thereof. The coating layer may be formed by using the coating elements among the above-mentioned compounds by using a suitable method (e.g., spraying, dipping, etc.) that does not adversely affect the physical properties of the cathode active material.
Suitable conductive substances may be used. The conductive substance may be, for example, carbon black, graphite particles, or 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, or the like.
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. At least one of the conductive substance, the binder and the solvent may be omitted depending on the intended use and configuration of the lithium battery.
The anode can be prepared by a suitable manufacturing method. For example, the anode active material composition may be 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 the membrane separated from the support may be laminated onto a metal current collector to complete the fabrication of the anode plate.
As the anode active material, a suitable anode active material for a lithium battery can be used. For example, the anode active material may include at least one selected from the group consisting of lithium metal, a metal that can be alloyed with lithium, a transition metal oxide, a non-transition metal oxide, and a carbonaceous material.
For example, the metal alloyable with lithium can be Si, Sn, Al, Ge, lead (Pb), bismuth (Bi), antimony (Sb), Si-Y 'alloys (Y' is an alkali metal, an alkaline earth metal, a group 13 and group 14 element, a transition metal, a rare earth element, or combinations thereof, and is not Si), Sn-Y 'alloys (Y' is an alkali metal, an alkaline earth metal, a group 13 and group 14 element, a transition metal, a rare earth element, or combinations thereof), andelement or a combination thereof, and not Sn). The element Y' is selected from Mg, Ca, Sr, barium (Ba), radium (Ra), Sc, Y, Ti, Zr, hafnium (Hf),
Figure BDA0002046741130000191
(Rf), V, niobium (Nb), tantalum (Ta),
Figure BDA0002046741130000192
(Db), Cr, Mo, tungsten (W),
Figure BDA0002046741130000193
(Sg), technetium (Tc), rhenium (Re),
Figure BDA0002046741130000194
(Bh), Fe, Pb, ruthenium (Ru), osmium (Os),
Figure BDA0002046741130000195
(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 can be SnO2、SiOx(wherein 0)<x<2) And the like.
For example, the carbonaceous material may be crystalline carbon, amorphous carbon, or a mixture thereof. Examples of the crystalline carbon include natural graphite and artificial graphite each having an irregular shape or in the form of a plate, a flake, 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. At least one of the conductive substance, the binder and the solvent may be omitted depending on the intended use and configuration of the lithium battery.
A suitable separator to be disposed between the cathode and the anode can be prepared. As the separator, a separator having low resistance to ion migration in the electrolyte and high electrolyte retention capacity may 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 windable 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 can be manufactured according to the following method.
The polymer resin, filler and solvent may be mixed together to prepare a separator composition. The separator composition can then be coated directly onto the electrode and dried to form the separator. In one embodiment, the separator composition may be cast onto a support and dried, and then a separator film separated from the support may be laminated onto the 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 a vinylidene fluoride/hexafluoropropylene copolymer, PVDF, polyacrylonitrile, polymethyl methacrylate, mixtures thereof, and the like.
The organic electrolyte solution as described above may be prepared.
As shown in fig. 7, the lithium battery 1 may include a cathode 3, an anode 2, and a separator 4. The cathode 3, the anode 2, and the separator 4 may be wound or folded and then accommodated in the battery case 5. Subsequently, an organic electrolyte solution may be injected into the battery case 5, and the battery case 5 may be 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.
In some embodiments, the separator 4 may be disposed between the cathode 3 and the anode 2 to form a battery assembly, a plurality of battery assemblies may be stacked in a bicell structure and impregnated with an organic electrolyte solution, and the resultant may be put in a pouch and sealed, thereby completing the manufacture of a lithium battery.
The battery modules may be stacked to form a battery pack, and 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 Electric Vehicles (EVs). For example, the lithium battery may be used in a hybrid vehicle, such as a plug-in hybrid electric vehicle (PHEV) or the like. Lithium batteries are also used in areas where large amounts of electricity need 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 examples and comparative examples should not be construed as limiting the scope of the embodiments, nor should comparative examples be construed as being outside of the scope of the embodiments. Further, it is 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 Compounds of formula 6
The compound of formula 6 can be prepared according to the following reaction scheme 1:
< reaction scheme 1>
Figure BDA0002046741130000211
Synthesis of Compound A
68.0g (0.499mol) of pentaerythritol and 100g of molecular sieve (type 4A) are added to a volume ratio of 1:1 of Tetrahydrofuran (THF) and dichloromethane (DCM, CH)2Cl2) And the resulting solution was refluxed for 20 minutes. Subsequently, 110ml (2.8 equiv., 1.40mol) of sulfinyl chloride (SOCl) are introduced2) To the resultant was added, and the resultant solution was refluxed for 8 hours until pentaerythritol was completely consumed by the reaction, thereby obtaining a pale yellow solution. The resulting light yellow solution was filtered and concentrated to give a residue containing a light yellow solid. Thereafter, 1L of saturated sodium bicarbonate (NaHCO)3) The solution was added directly to the residue at a rate that minimizes effervescence to give a suspension. The suspension was stirred vigorously 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 the air, thereby obtaining 104.61g (0.458mol) of Compound A (yield: 92%).
Of Compound A1H-NMR and13the 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 to prepare an electrolyte solution.
< formula 6>
Figure BDA0002046741130000212
Preparation of organic electrolyte solution
Example 1: SEI-13161.0 wt.%
0.90M LiPF as lithium salt6And 1 wt% of the compound of formula 6 was added to a mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) in a volume ratio of 3:5:2 to prepare an organic electrolyte solution.
< formula 6>
Figure BDA0002046741130000221
Example 2: SEI-13161.0 wt% + VC 0.5 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that 1 wt% of the compound of formula 6 and 0.5 wt% of Vinylene Carbonate (VC) were used as additives.
Example 3: SEI-13160.5 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 4: SEI-13160.2 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 0.2 wt%.
Example 5: SEI-13160.3 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 0.3 wt%.
Example 6: SEI-13160.7 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 0.7 wt%.
Example 7: SEI-13161.5 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 1.5 wt%.
Example 8: SEI-13162 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 2 wt%.
Example 9: SEI-13163 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 3 wt%.
Example 9 a: SEI-13164 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 4 wt%.
Example 10: SEI-13165 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 5 wt%.
Comparative example 1: SEI-13160 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the compound of formula 6 used as an additive was not used.
Production of lithium batteries (examples 1-1 to 3-1 and comparative example 1-1)
Examples 1 to 1
Manufacture of anodes
98 wt% of artificial graphite (BSG-L manufactured by Tianjin BTR New Energy Technology co., ltd.), 1.0 wt% of styrene-butadiene rubber (SBR) as a binder (manufactured by Zeon) and 1.0 wt% 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 on 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 hour, followed by further drying under the following conditions: and vacuum-processed at 120 c for 4 hours, and roll-pressed, thereby completing the fabrication of the anode plate.
Manufacture of cathodes
97.45 weight percent of LiNi1/3Co1/3Mn1/3O20.5 wt% of powder type artificial graphite (SFG 6 manufactured by Timcal), 0.7 wt% of carbon black (ketjen black manufactured by ECP), 0.25 wt% of modified acrylonitrile rubber (BM-720H manufactured by Zeon Corporation), 0.9 wt% of polyvinylidene fluoride (PVDF, S6020 manufactured by Solvay), and 0.2 wt% of PVDF (S5130 manufactured by Solvay) as conductive substances were mixed together, 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 on 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 hour, followed by further drying under the following conditions: and vacuum-processed at 120 c for 4 hours, and roll-pressed, thereby completing the manufacture of the cathode plate.
A polyethylene separator (manufactured by SK Innovation) having a thickness of 14 μm, the cathode side of which was coated with ceramic, and the organic electrolyte solution prepared according to example 1 were used to complete the manufacture 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 respectively used instead of the organic electrolyte solution of example 1.
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 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 of 0.1C rate until the voltage reached 4.25V (with respect to Li), and then, while maintaining a constant voltage of 4.25V, the charging process was interrupted with a current of 0.05C rate. Subsequently, each lithium battery was discharged at a constant current of 0.1C rate until the voltage reached 2.8V (relative to Li) (formation operation, first cycle).
Each lithium cell after the first cycle of the forming operation was charged at 25C with a constant current of 0.2C rate until the voltage reached 4.25V (vs. Li), and then the charging process was shut off with a current of 0.05C rate while maintaining a constant voltage of 4.25V. Subsequently, each lithium battery was discharged at a constant current of 0.2C rate until the voltage reached 2.8V (with respect to Li) (formation operation, second cycle).
Each lithium cell after the second cycle of the forming operation was charged at 25C with a constant current of 1.0C rate until the voltage reached 4.25V (vs. Li), and then the charging process was shut off with a current of 0.05C rate while maintaining a constant voltage of 4.25V. Subsequently, each lithium battery was discharged at a constant current of 1.0C rate 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 a10 minute rest time at the end of each charge/discharge cycle.
A portion of the charge and discharge experimental results are shown in table 1 below and in fig. 1 and 2. The capacity retention at the 380 th cycle is defined using the following equation 1:
equation 1
Capacity retention rate [ 380 th cycle discharge capacity/1 st cycle discharge capacity ] × 100
TABLE 1
Discharge capacity [ mAh/g ] at 380 th cycle] Capacity retention rate of 380 th cycle [% ]]
Examples 1 to 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 include the additive according to the 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 does not include such an additive.
Evaluation example 2: evaluation of Charge and discharge characteristics at 4.25V and high temperature (45 ℃ C.)
The lithium batteries of examples 1-1 to 3-1 and comparative example 1-1 were evaluated for charge and discharge characteristics 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 experiment results are shown in table 2 below and in fig. 3 and 4. The capacity retention for the 200 th cycle is defined using equation 2 below:
equation 2
Capacity retention rate ═ discharge capacity at 200 th cycle/discharge capacity at 1 st cycle ] × 100
TABLE 2
Discharge capacity [ mAh/g ] at 200 th cycle] Capacity retention rate of 200 th cycle [% ]]
Examples 1 to 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, which include the additive according to the embodiment of the present disclosure, exhibited significantly enhanced discharge capacity and life characteristics at high temperatures, as compared to the lithium battery of comparative example 1-1, which does not include such an additive.
Evaluation example 3: evaluation of Charge and discharge characteristics at 4.30V and 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 of 0.1C rate until the voltage reached 4.30V (with respect to Li), and then, while maintaining a constant voltage of 4.30V, the charging process was interrupted with a current of 0.05C rate. Subsequently, each lithium battery was discharged at a constant current of 0.1C rate until the voltage reached 2.8V (relative to Li) (formation operation, first cycle).
Each lithium cell after the first cycle of the forming operation was charged at 25C with a constant current of 0.2C rate until the voltage reached 4.30V (vs. Li), and then the charging process was shut off with a current of 0.05C rate while maintaining a constant voltage of 4.30V. Subsequently, each lithium battery was discharged at a constant current of 0.2C rate until the voltage reached 2.8V (with respect to Li) (formation operation, second cycle).
Each lithium cell after the second cycle of the forming operation was charged at 25C with a constant current of 0.5C rate until the voltage reached 4.30V (vs. Li), and then the charging process was shut off with a current of 0.05C rate while maintaining a constant voltage of 4.30V. Subsequently, each lithium battery was discharged at a constant current of 1.0C rate 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 a10 minute rest time at the end of each charge/discharge cycle.
A portion of the charge and discharge experiment results are shown in table 3 and fig. 5 below. The capacity retention at cycle 250 is defined using equation 3 below:
equation 3
Capacity retention rate ═ discharge capacity at 250 th cycle/discharge capacity at 1 st cycle ] × 100
TABLE 3
Discharge capacity [ mAh/g ] at 250 th cycle] Capacity retention rate of 250 th cycle [% ]]
Examples 1 to 1 171 84
Comparative example 1-1 154 77
As shown in table 3 and fig. 5, the lithium batteries of examples 1-1, which include the additive according to the embodiments of the present disclosure, exhibited significantly enhanced discharge capacity and life characteristics at room temperature, as compared to the lithium batteries of comparative examples 1-1, which do not include such an additive.
Evaluation example 4: evaluation of Charge and discharge characteristics at 4.30V and high temperature (45 ℃ C.)
The lithium batteries of example 1-1 and comparative example 1-1 were evaluated for charge and discharge characteristics using the same method as 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 portion of the charge and discharge experiment results are shown in table 4 and fig. 6 below. The capacity retention for the 200 th cycle is defined using equation 4 below:
equation 4
Capacity retention rate ═ discharge capacity at 200 th cycle/discharge capacity at 1 st cycle ] × 100
TABLE 4
Discharge capacity [ mAh/g ] at 200 th cycle] Capacity retention rate of 200 th cycle [% ]]
Examples 1 to 1 189 90
Comparative example 1-1 174 84
As shown in table 4 and fig. 6, the lithium batteries of examples 1-1, which include the additive according to the embodiments of the present disclosure, exhibited significantly enhanced discharge capacity and life characteristics at high temperatures, as compared to the lithium batteries of comparative examples 1-1, which do not include such an 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 the first charge and discharge cycles as follows. Each lithium battery was charged at a constant current of 0.5C rate at 25C until the voltage reached 4.3V, and then, while maintaining a constant voltage of 4.3V, each lithium battery was charged until the current reached 0.05C, and then discharged at a constant current of 0.5C rate until the voltage reached 2.8V.
Each lithium cell 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 charged with a constant voltage of 4.3V until the current reached 0.05C, and then discharged with a constant current of 0.2C rate until the voltage reached 2.8V.
Each lithium cell was subjected to a third 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 charged with a constant voltage of 4.3V until the current reached 0.05C, 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 a standard capacity.
Each lithium cell was subjected to a fourth charge and discharge cycle as follows. Each lithium battery was charged at a rate of 0.5C until the voltage reached 4.30V, then, while maintaining a constant voltage of 4.30V, each lithium battery was charged until the current reached 0.05C, the charged batteries were stored in an oven at 60 ℃ for 10 days and 30 days, then the batteries were taken out of the oven, and then discharged at a rate of 0.1C until the voltage reached 2.80V.
A portion 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 rate after high-temperature storage [% ] x100 [ high-temperature discharge capacity/standard capacity at 4 th cycle ] (herein, standard capacity is discharge capacity at 3 rd cycle)
TABLE 5
Capacity retention after 10 days of storage [% ]] Capacity retention after 30 days of storage [% ]]
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, as compared to the lithium battery of comparative example 1-1 not including the organic electrolyte solution of the present disclosure.
Evaluation example 6: evaluation of direct Current internal resistance (DC-IR) after high temperature (60 ℃ C.) storage
The DC-IR of each lithium battery of examples 1-1 to 3-1 and comparative example 1-1 before being placed in an oven at 60 ℃, after being stored in the oven at 60 ℃ for 10 days, and after being stored in the oven at 60 ℃ for 30 days was measured at room temperature (25 ℃) using the following method.
Each lithium cell was subjected to a first charge and discharge cycle as follows. Each lithium battery was charged with 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, each lithium battery was subjected to the following treatments: discharging at a constant current of 0.5C for 30 seconds and then standing for 30 seconds, and charging at a constant current of 0.5C for 30 seconds and then standing for 10 minutes; discharging at a constant current of 1.0C for 30 minutes, then standing for 30 seconds, and charging at a constant current of 0.5C for 1 minute, then standing for 10 minutes; discharging at a constant current of 2.0C for 30 seconds and then standing for 30 seconds, and charging at a constant current of 0.5C for 2 minutes and then standing for 10 minutes; discharged at a constant current of 3.0C for 30 seconds and then left to stand for 30 seconds, and charged at a constant current of 0.5C for 2 minutes and then left to stand for 10 minutes.
The average voltage drop at each C-rate for 30 seconds is the dc voltage value.
A part of the increase in the dc internal resistance calculated from the measured initial dc internal resistance and the dc internal resistance after the high-temperature storage is shown in table 6 below. The dc internal resistance increase is represented by the following equation 6:
equation 6
Dc internal resistance increase [% ] x100 [ dc internal resistance after high-temperature storage/initial dc internal resistance ]
TABLE 6
Figure BDA0002046741130000281
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 exhibited a decrease in increase in direct current internal resistance after high-temperature storage, as compared to the lithium battery of comparative example 1-1 not including the organic electrolyte solution.
Production of lithium batteries (examples A1 to A11, reference examples A1 to A5 and comparative examples A1 to A3)
Example a 1: NCM, Ni60+ SEI-13160.5 wt.%
Manufacture of anodes
98 wt% of artificial graphite (BSG-L manufactured by Tianjin BTR New Energy Technology co., ltd.), 1.0 wt% of SBR (manufactured by Zeon) as a binder, and 1.0 wt% of CMC (manufactured by NIPPON a & L) were mixed together, the mixture was added to distilled water, and the resulting solution was stirred for 60 minutes using a mechanical stirrer to prepare an anode active material slurry. The anode active material slurry was coated on 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 hour, and then further vacuum-dried at 120 ℃ for 4 hours, and subjected to roll pressing, thereby completing the fabrication of an anode plate.
Manufacture of cathodes
97.45 wt% of Li1.02Ni0.60Co0.20Mn0.20O20.5 wt% of powder type artificial graphite (SFG 6 manufactured by Timcal), 0.7 wt% of carbon black (ketjen black manufactured by ECP), 0.25 wt% of modified acrylonitrile rubber (BM-720H manufactured by Zeon corporation), 0.9 wt% of PVDF (S6020 manufactured by Solvay) and 0.2 wt% of PVDF (S5130 manufactured by Solvay) as conductive substances were mixed together, 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 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 hour, and then further vacuum-dried at 120 ℃ for 4 hours, and subjected to roll pressing, thereby completing the manufacture of a cathode plate.
The manufacture of a lithium battery was completed using a polyethylene separator having a thickness of 14 μm and having a cathode side coated with ceramic, and the organic electrolyte solution prepared according to example 3.
Example a 2: NCM, Ni60+ SEI-13160.7 wt.%
A lithium battery was fabricated in the same manner as in example a1, except that the organic electrolyte solution prepared according to example 6 was used instead of the organic electrolyte solution of example 3.
Example a 3: NCM, Ni60+ SEI-13161 wt.%
A lithium battery was fabricated in the same manner as in example a1, except that the organic electrolyte solution prepared according to example 1 was used instead of the organic electrolyte solution of example 3.
Example a 4: NCM, Ni60+ SEI-13161.5 wt.%
A lithium battery was fabricated in the same manner as in example a1, except that the organic electrolyte solution prepared according to example 7 was used instead of the organic electrolyte solution of example 3.
Example a 5: NCM, Ni60+ SEI-13163 wt.%
A lithium battery was fabricated in the same manner as in example a1, except that the organic electrolyte solution prepared according to example 9 was used instead of the organic electrolyte solution of example 3.
Example a 6: NCM, Ni88+ SEI-13161 wt.%
Except using Li1.02Ni0.88Co0.08Mn0.04O2In place of Li1.02Ni0.60Co0.20Mn0.20O2A lithium battery was produced in the same manner as in example a1, except that the electrolyte solution of example 1 was used as the electrolyte solution as the cathode active material.
Example a 7: NCA, Ni88+ SEI-13160.5 wt.%
Except using Li1.02Ni0.88Co0.08Al0.04O2In place of Li1.02Ni0.60Co0.20Mn0.20O2A lithium battery was fabricated in the same manner as in example a1, except for using as a cathode active material.
Example A8: NCA, Ni88+ SEI-13160.7 wt.%
Except using Li1.02Ni0.88Co0.08Al0.04O2In place of Li1.02Ni0.60Co0.20Mn0.20O2A lithium battery was produced in the same manner as in example a1, except that the electrolyte solution of example 6 was used as the electrolyte solution as the cathode active material.
Example a 9: NCA, Ni88+ SEI-13161 wt.%
Except using Li1.02Ni0.88Co0.08Al0.04O2In place of Li1.02Ni0.60Co0.20Mn0.20O2A lithium battery was produced in the same manner as in example a1, except that the electrolyte solution of example 1 was used as the electrolyte solution as the cathode active material.
Example a 10: NCA, Ni88+ SEI-13163 wt.%
Except using Li1.02Ni0.88Co0.08Al0.04O2In place of Li1.02Ni0.60Co0.20Mn0.20O2As cathode active material, and use of electrolyte prepared according to example 9A lithium battery was fabricated in the same manner as in example a1, except that the solution was used as an electrolyte solution.
Example a 11: NCA, Ni91+ SEI-13161 wt.%
Except using Li1.02Ni0.91Co0.05Al0.04O2In place of Li1.02Ni0.60Co0.20Mn0.20O2A lithium battery was produced in the same manner as in example a1, except that the electrolyte solution of example 1 was used as the electrolyte solution as the cathode active material.
Reference example a 1: ni55+ SEI-13161 wt.%
Except using Li1.02Ni0.55Co0.25Mn0.20O2In place of Li1.02Ni0.60Co0.20Mn0.20O2A lithium battery was produced in the same manner as in example a1, except that the electrolyte solution of example 1 was used as the electrolyte solution as the cathode active material.
Reference example a 2: NCM, Ni60+ SEI-13160.2 wt.%
A lithium battery was fabricated in the same manner as in example a1, except that the organic electrolyte solution prepared according to example 4 was used instead of the organic electrolyte solution of example 3.
Reference example a 3: NCM, Ni60+ SEI-13165 wt.%
A lithium battery was fabricated in the same manner as in example a1, except that the organic electrolyte solution prepared according to example 10 was used instead of the organic electrolyte solution of example 3.
Reference example a 4: NCA, Ni88+ SEI-13160.2 wt.%
Except using Li1.02Ni0.88Co0.08Al0.04O2In place of Li1.02Ni0.60Co0.20Mn0.20O2As a cathode active material, a lithium battery was fabricated in the same manner as in example a1, except that the electrolyte solution prepared according to example 4 was used in place of the organic electrolyte solution of example 3.
Reference example a 5: NCA, Ni88+ SEI-13165 wt.%
Except using Li1.02Ni0.88Co0.08Al0.04O2In place of Li1.02Ni0.60Co0.20Mn0.20O2A lithium battery was produced in the same manner as in example a1, except that the electrolyte solution of example 10 was used instead of the organic electrolyte solution of example 3 as a cathode active material.
Comparative example a 1: ni60+ SEI-13160 wt.%
A lithium battery was fabricated in the same manner as in example a1, except that the organic electrolyte solution prepared according to comparative example 1 was used instead of the organic electrolyte solution of example 3.
Comparative example a 2: LCO, Ni00+ SEI-13161 wt.%
Except that LiCoO is used2In place of Li1.02Ni0.60Co0.20Mn0.20O2A lithium battery was produced in the same manner as in example a1, except that the organic electrolyte solution of example 1 was used as the electrolyte solution as the cathode active material.
Comparative example a 3: NCM + LMO + SEI-13161 wt.%
Except that LiNi was used in a weight ratio of 1:11/3Co1/3Mn1/3O2And LiMn2O4In place of Li1.02Ni0.85Co0.10Mn0.05O2A lithium battery was produced in the same manner as in example a1, except that the organic electrolyte solution of example 1 was used as the electrolyte solution as the cathode active material.
Evaluation example a 1: evaluation of Charge/discharge characteristics at 4.25V and Room temperature (25 ℃ C.)
The lithium batteries manufactured according to examples a1 to a11, reference examples a1 to a5, and comparative examples a1 to A3 were evaluated for charge/discharge characteristics using the same method as that used in evaluation example 1.
A portion of the charge and discharge test results are shown in table a1 below. The capacity retention at the 380 th cycle is defined using the following equation 1:
equation 1
Capacity retention rate [ 380 th cycle discharge capacity/1 st cycle discharge capacity ] × 100
TABLE A1
Capacity retention rate of 380 th cycle [% ]]
Example A1(NCM, Ni60+ SEI-13160.5 wt%) 94
Example A2(NCM, Ni60+ SEI-13160.7 wt%) 94
Example A3(NCM, Ni60+ SEI-13161 wt%) 95
Example A4(NCM, Ni60+ SEI-13161.5 wt%) 95
Example A5(NCM, Ni60+ SEI-13163 wt%) 93
Example A6(NCM, Ni88+ SEI-13161 wt%) 94
Example A7(NCA, Ni88+ SEI-13160.5 wt%) 93
Example A8(NCA, Ni88+ SEI-13160.7 wt%) 94
Example A9(NCA, Ni88+ SEI-13161 wt%) 94
Example A10(NCA, Ni88+ SEI-13163 wt%) 92
Example A11(NCA, Ni91+ SEI-13161 wt%) 93
Reference example A1(NCM, Ni55+ SEI-13161 wt%) 90
Reference example A2(NCM, Ni60+ SEI-13160.2 wt%) 92
Reference example A3(NCM, Ni60+ SEI-13165 wt%) 93
Reference example A4(NCA, Ni88+ SEI-13160.2 wt%) 93
Reference example A5(NCA, Ni88+ SEI-13165 wt%) 91
Comparative example A1(NCM, Ni60+ SEI-13160 wt%) 85
Comparative example A2(LCO, Ni00+ SEI-13161 wt%) 83
Comparative example A3(NCM + LMO + SEI-13161 wt%) 85
As shown in table a1, the lithium batteries of examples a1 to a11 of the present disclosure, which include an additive and a cathode active material having a high nickel content, exhibited significantly enhanced life characteristics at room temperature, as compared to the lithium batteries of comparative examples a1 to A3, which include cathode active materials having a low nickel content or no additive.
In addition, the lithium batteries of examples a1 to a11, each including an amount of the additive, exhibited more enhanced life characteristics at room temperature than the lithium batteries of reference examples a2 to a5, each including an amount of the additive outside a certain range.
Evaluation example a 2: evaluation of direct Current-internal resistance (DC-IR) after high temperature (60 ℃ C.) storage
The DC-IR after high-temperature storage of the lithium batteries of examples a1 to a11, reference examples a1 to a5, and comparative examples a1 to A3 was measured using the same method as that used in evaluation example 6.
A portion of the increase in DC-IR obtained by calculation using the measured initial DC-IR and the measured DC-IR after high temperature storage is shown in Table A2 below. The DC-IR increase is represented by the following equation 6:
equation 6
Direct current internal resistance increase [% ] x100 [ direct current internal resistance after high-temperature storage/initial direct current internal resistance ] ×
TABLE A2
Figure BDA0002046741130000321
Figure BDA0002046741130000331
As shown in table a2, the lithium batteries of examples a1 to a11 of the present disclosure, which include an additive and a cathode active material having a high nickel content, exhibited lower DC-IR increase than each of the lithium batteries of comparative examples a1 to A3, which include a cathode active material having a low nickel content and no additive.
Further, the lithium batteries of examples a1 to a11, which included an amount of the additive, exhibited lower DC-IR increase than each of the lithium batteries of reference examples a1 to a5, which included an amount of the additive outside of a certain range.
As is apparent from the foregoing description, a lithium battery including a cathode of a lithium transition metal oxide having a high nickel content and an organic electrolyte solution containing a novel bicyclic sulfate-based additive may exhibit enhanced high temperature characteristics and life characteristics.
By way of summary and review, aqueous electrolyte solutions that are highly reactive with lithium may not be suitable for use in lithium batteries when such batteries are operated at high operating voltages. Lithium batteries typically use an organic electrolyte solution. 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, an irreversible reaction of overusing charge due to a side reaction between an anode/cathode and the organic electrolyte solution may occur during initial charge. Due to such an 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 SEI layers and/or protective layers 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 invention provide a lithium battery including: a cathode comprising a lithium transition metal oxide having a high nickel content; 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 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 purposes of limitation. In some instances, features, characteristics, and/or elements described in connection with a particular embodiment may be used alone, or in combination with features, characteristics, and/or elements described in connection with other embodiments, as will be apparent to one of ordinary skill in the art at the time of filing the present application, unless otherwise explicitly stated. It will, therefore, 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 of the invention as set forth in the appended claims.

Claims (19)

1. A lithium battery, comprising:
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 active material includes a nickel-containing layered lithium transition metal oxide, the content of nickel in the lithium transition metal oxide is 60 mol% or more with respect to the total number of moles of transition metals in the lithium transition metal oxide, 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:
< formula 1>
Figure FDA0002046741120000011
Wherein, in formula 1, A1、A2、A3And A4Each independently being a covalent bond, substituted or unsubstituted C1-C5Alkylene, carbonyl or sulfinyl, in which A1And A2Are not all covalent bonds, and A3And A4Not all are covalent bonds.
2. A lithium battery as claimed in claim 1, wherein a1、A2、A3And A4At least one of which is unsubstituted or substituted C1-C5Alkylene, wherein said substituted C1-C5The substituent of the alkylene group is at least one selected from the group consisting of: halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen-substituted or unsubstituted C3-C20Heterocyclic radical, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl or a polar functional group having at least one heteroatom.
3. A lithium battery as claimed in claim 1, wherein a1、A2、A3And A4At least one of which is unsubstituted or substituted C1-C5Alkylene, wherein said substituted C1-C5The substituent of the alkylene group is halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
4. A lithium battery as in claim 2, wherein said substituted C is1-C5The substituent of alkylene includes the polar functional group having at least one hetero atom, wherein the polar functional group is at least one selected from the group consisting of: -F, -Cl, -Br, -I, -C (═ O) OR16、-OR16、-OC(＝O)OR16、-R15OC(＝O)OR16、-C(＝O)R16、-R15C(＝O)R16、-OC(＝O)R16、-R15OC(＝O)R16、-C(＝O)-O-C(＝O)R16、-R15C(＝O)-O-C(＝O)R16、-SR16、-R15SR16、-SSR16、-R15SSR16、-S(＝O)R16、-R15S(＝O)R16、-R15C(＝S)R16、-R15C(＝S)SR16、-R15SO3R16、-SO3R16、-NNC(＝S)R16、-R15NNC(＝S)R16、-R15N＝C＝S、-NCO、-R15-NCO、-NO2、-R15NO2、-R15SO2R16、-SO2R16、
Figure FDA0002046741120000021
Figure FDA0002046741120000022
Wherein, in the above formula, R11And R15Each independently halogen substituted or unsubstituted C1-C20Alkylene, halogen substituted or unsubstituted C2-C20Alkenylene, halogen substituted or unsubstituted C2-C20Alkynylene, halogen substituted or unsubstituted C3-C12Cycloalkylene, halogen substituted or unsubstituted C6-C40Arylene, halogen substituted or unsubstituted C2-C40Heteroarylene, halogen substituted or unsubstituted C7-C15Alkylarylene or halogen substituted or unsubstituted C7-C15An aralkylene group; and is
R12、R13、R14And R16Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C12Cycloalkyl, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl, halogen radicalsSubstituted or unsubstituted C7-C15Alkylaryl, halogen substituted or unsubstituted C7-C15Trialkylsilyl or halogen substituted or unsubstituted C7-C15An aralkyl group.
5. The lithium battery of claim 1, wherein the bicyclic sulfate-based compound is represented by formula 2 or formula 3:
Figure FDA0002046741120000031
wherein, in formula 2 and formula 3, B1、B2、B3、B4、D1And D2Each independently is-C (E)1)(E2) -, carbonyl or sulfinyl; and is
E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen substituted or unsubstituted C3-C20Heterocyclic radical, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
6. A lithium battery as in claim 5, wherein E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C10Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
7. A lithium battery as in claim 5, wherein E1And E2Each independently hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroEthyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
8. The lithium battery of claim 1, wherein the bicyclic sulfate-based compound is represented by formula 4 or formula 5:
Figure FDA0002046741120000032
wherein, in formula 4 and formula 5, R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
9. A lithium battery as in claim 8, wherein R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently hydrogen, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
10. The lithium battery of claim 1, wherein the bicyclic sulfate-based compound is represented by one of the following formulas 6 to 17:
Figure FDA0002046741120000041
11. the lithium battery as claimed in claim 1, wherein the amount of the bicyclic sulfate-based compound is 0.4 wt% or more and less than 5 wt% based on the total weight of the organic electrolyte solution.
12. The lithium battery of claim 1, wherein the amount of the bicyclic sulfate-based compound is 0.4 to 3 wt% based on the total weight of the organic electrolyte solution.
13. 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: LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiCF3SO3、Li(CF3SO2)2N、LiC4F9SO3、LiAlO2、LiAlCl4、LiN(CxF2x+1SO2)(CyF2y+1SO2) (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.
14. 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 halogen, cyano, and nitro, vinyl ethylene carbonate substituted with at least one substituent selected from halogen, cyano, and nitro, fluoroethylene carbonate substituted with at least one substituent selected from halogen, cyano, and nitro.
15. The lithium battery as claimed in claim 14, wherein the amount of the cyclic carbonate compound is 0.01 wt% to 5 wt% based on the total weight of the organic electrolyte solution.
16. The lithium battery of claim 1, wherein the organic electrolyte solution further comprises a second lithium salt that is different from the first lithium salt and is represented by one of the following formulas 18 to 25:
Figure FDA0002046741120000051
17. the lithium battery of claim 16, wherein the amount of the second lithium salt is 0.1 to 5 wt% based on the total weight of the organic electrolyte solution.
18. The lithium battery as claimed in claim 1, wherein the lithium transition metal oxide is represented by the following formula 26:
< formula 26>
LiaNixCoyMzO2-bAb
Wherein, in formula 26, a is not less than 1.0 and not more than 1.2, b is not less than 0 and not more than 0.2, x is not less than 0.6 and not more than 1, y is not less than 0.2 and 0 is not less than 0.2, and x + y + z is 1;
m is at least one selected from the following: manganese, vanadium, magnesium, gallium, silicon, tungsten, molybdenum, iron, chromium, copper, zinc, titanium, aluminum, and boron; and is
A is fluorine, sulfur, chlorine, bromine or a combination thereof.
19. The lithium battery as claimed in claim 1, wherein the lithium transition metal oxide is a compound represented by formula 27 or formula 28 below:
< formula 27>
LiNixCoyMnzO2
< formula 28>
LiNixCoyAlzO2
Wherein, in formulae 27 and 28, 0.6. ltoreq. x.ltoreq.0.95, 0< y.ltoreq.0.2, 0< z.ltoreq.0.2, and x + y + z is 1.
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