CN117747951A - Lithium battery - Google Patents

Lithium battery Download PDF

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Publication number
CN117747951A
CN117747951A CN202410134872.0A CN202410134872A CN117747951A CN 117747951 A CN117747951 A CN 117747951A CN 202410134872 A CN202410134872 A CN 202410134872A CN 117747951 A CN117747951 A CN 117747951A
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unsubstituted
halogen substituted
electrolyte solution
substituted
lithium battery
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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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

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Abstract

The lithium battery includes: cathode comprising cathode active materialA pole; 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 60mol% or more relative to the total moles of transition metal. The organic electrolyte solution includes a first lithium salt, an organic solvent, and a bicyclic sulfate-based compound represented by the following formula 1:<1 (1)>Wherein in formula 1, A 1 、A 2 、A 3 And A 4 Each independently is a covalent bond, a substituted or unsubstituted C1-C5 alkylene, carbonyl, or sulfinyl group, wherein A 1 And A 2 Not all are covalent bonds, and A 3 And A 4 Not all covalent bonds.

Description

Lithium battery
Description of the division
The present application is a divisional application of the patent application of the invention with the application date of 2019, 4-month and 30-date, the national application number of 201910360743.2 and the invention name of "lithium battery".
Cross Reference to Related Applications
U.S. patent application Ser. No. 15/422,873 entitled "lithium Battery," filed on even date 19 at 9 in 2018, continues to claim 16/135,301, the entire contents of which are incorporated herein by reference.
Technical Field
Various embodiments of the present invention relate to lithium batteries.
Background
Lithium batteries are used as driving power sources for portable electronic devices including video cameras, mobile phones, notebook computers, and the like. The lithium secondary battery can be recharged at a high rate and has an energy density per unit weight at least three times that of the existing lead storage battery, nickel-cadmium battery, nickel-hydrogen battery or nickel-zinc battery.
Disclosure of Invention
Various embodiments of the present invention relate to a lithium battery including: a cathode comprising a cathode active material, an anode comprising an anode active material, and an organic electrolyte solution between the cathode and the anode. The cathode active material includes a nickel-containing layered lithium transition metal oxide. The nickel content in the lithium transition metal oxide is about 60mol% or more relative to the total moles of transition metal 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:
< 1>
Wherein in formula 1, A 1 、A 2 、A 3 And A 4 Each independently is a covalent bond, substituted or unsubstituted C 1 -C 5 Alkylene, carbonyl or sulfinyl, wherein A 1 And A 2 Not all are covalent bonds, and A 3 And A 4 Not all covalent bonds.
A 1 、A 2 、A 3 And A 4 At least one of which is unsubstituted or substituted C 1 -C 5 Alkylene group, wherein substituted C 1 -C 5 The substituent of the alkylene group is at least one selected from the following: halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen-substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl or a polar functional group having at least one heteroatom.
A 1 、A 2 、A 3 And A 4 At least one of which is unsubstituted or substituted C 1 -C 5 Alkylene group, wherein substituted C 1 -C 5 The substituent of the alkylene group is halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
The 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) OR 16 、-OR 16 、-OC(＝O)OR 16 、-R 15 OC(＝O)OR 16 、-C(＝O)R 16 、-R 15 C(＝O)R 16 、-OC(＝O)R 16 、-R 15 OC(＝O)R 16 、-C(＝O)-O-C(＝O)R 16 、-R 15 C(＝O)-O-C(＝O)R 16 、-SR 16 、-R 15 SR 16 、-SSR 16 、-R 15 SSR 16 、-S(＝O)R 16 、-R 15 S(＝O)R 16 、-R 15 C(＝S)R 16 、-R 15 C(＝S)SR 16 、-R 15 SO 3 R 16 、-SO 3 R 16 、-NNC(＝S)R 16 、-R 15 NNC(＝S)R 16 、-R 15 N＝C＝S、-NCO、-R 15 -NCO、-NO 2 、-R 15 NO 2 、-R 15 SO 2 R 16 、-SO 2 R 16 、 Wherein, in the above formula, R 11 And R is 15 Each independently is halogen substituted or unsubstituted C 1 -C 20 Alkylene, halogen substituted or unsubstituted C 2 -C 20 Alkenylene, halogen substituted or unsubstituted C 2 -C 20 Alkynylene, halogen substituted or unsubstituted C 3 -C 12 Cycloalkylene, halogen substituted or unsubstituted C 6 -C 40 Arylene, halogen substituted or unsubstituted C 2 -C 40 Heteroarylene, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl or halogen substituted or unsubstituted C 7 -C 15 An aralkylene group; and R is 12 、R 13 、R 14 And R is 16 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 12 Cycloalkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groupHalogen substituted or unsubstituted C 7 -C 15 Alkylaryl, halogen substituted or unsubstituted C 7 -C 15 Trialkylsilyl or halogen substituted or unsubstituted C 7 -C 15 Aralkyl group, and->Representing the binding site to an adjacent atom.
The bicyclic sulfate based compound may be represented by formula 2 or 3:
wherein in formulas 2 and 3, B 1 、B 2 、B 3 、B 4 、D 1 And D 2 Each independently is-C (E) 1 )(E 2 ) -carbonyl or sulfinyl; and E is 1 And E is 2 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
E 1 And E is 2 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 10 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
E 1 And E is 2 Can 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:
wherein in formula 4 and formula 5, R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 May each independently be hydrogen, F, cl, br, I, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
The bicyclic sulfate-based compound may be represented by one of the following formulas 6 to 17:
The amount of the compound based on the bicyclic sulfate may be about 0.4wt% to about 5wt% based on the total weight of the organic electrolyte solution.
The amount of the compound based on the bicyclic sulfate may be about 0.4wt% to about 3wt% based on the total weight of the organic electrolyte solution.
The first lithium salt in the organic electrolyte solution may include a selection ofFrom at least one of the following: liPF (LiPF) 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiClO 4 、LiCF 3 SO 3 、Li(CF 3 SO 2 ) 2 N、LiC 4 F 9 SO 3 、LiAlO 2 、LiAlCl 4 、LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) (wherein x is more than or equal to 2 and less than or equal to 20, and y is more than or equal to 2 and less than or equal to 20), liCl and LiI.
The organic electrolyte solution may further comprise a cyclic carbonate compound, wherein the cyclic carbonate compound is selected from Vinylene Carbonate (VC), and is selected from halogen, cyano (-CN), and nitro (-NO) 2 ) VC, vinyl Ethylene Carbonate (VEC), substituted by at least one substituent selected from the group consisting of halogen, -CN and-NO 2 VEC substituted with at least one substituent of (C), fluoroethylene carbonate (FEC), and halogen, -CN and-NO 2 FEC substituted by at least one substituent of (a).
The amount of the cyclic carbonate compound may be about 0.01wt% to about 5wt% based on the total weight of the organic electrolyte solution.
The organic electrolyte solution may further comprise a second lithium salt, which is different from the first lithium salt, and is formed of
One of formulas 18 to 25:
The amount of the second lithium salt may be about 0.1wt% to about 5wt% based on the total weight of the organic electrolyte solution.
The lithium transition metal oxide may be represented by the following formula 26:
< 26>
Li a Ni x Co y M z O 2-b A b
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 the following formula 27 or formula 28:
< 27>
LiNi x Co y Mn z O 2
< 28>
LiNi x Co y Al z O 2
Wherein in formulas 27 and 28, 0.6.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.2, 0< z.ltoreq.0.2, and x+y+z=1.
Lithium batteries may have a high voltage of about 3.8V or higher.
Drawings
The various features will become apparent to those skilled in the art from the detailed description of the exemplary embodiments with reference to the accompanying drawings, in which:
fig. 1 shows graphs showing discharge capacities at room temperature of lithium batteries manufactured according to examples 1-1 and 2-1 and comparative example 1-1;
fig. 2 shows graphs showing capacity retention rates at room temperature of lithium batteries of examples 1-1 and 2-1 and comparative example 1-1;
Fig. 3 shows graphs showing discharge capacities of lithium batteries of examples 1-1 and 2-1 and comparative example 1-1 at high temperatures;
fig. 4 shows graphs showing capacity retention rates at high temperatures of the lithium batteries of examples 1-1 and 2-1 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 also provided with
Fig. 7 shows a view of a lithium battery according to an embodiment.
Detailed Description
Exemplary embodiments will now be described more fully hereinafter with reference to the accompanying drawings; however, they may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the exemplary embodiments to those skilled in the art.
The lithium battery according to an embodiment includes: a cathode including a cathode active material, an anode including 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 60mol% or more relative to the total moles of transition metal. 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:
< 1>
Wherein in formula 1, A 1 、A 2 、A 3 And A 4 Each independently is a covalent bond, substituted or unsubstituted C 1 -C 5 Alkylene, carbonyl or sulfinyl, wherein A 1 And A 2 Not all are covalent bonds, and A 3 And A 4 Not all covalent bonds.
An organic electrolyte solution including a dicyclic sulfate-based compound as an additive for lithium batteries can enhance battery performance, such as high temperature characteristics, lifetime 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 60mol% or more with respect to the total mole number 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 lithium batteries by adding a biscyclosulfate based compound to the electrolyte solution will now be described in further detail.
When the dicyclic sulfate-based compound is included in the electrolyte solution, the sulfate group of the dicyclic sulfate-based compound may be reduced by itself by accepting electrons from the anode surface during charging, or may react with polar solvent molecules previously reduced, thereby affecting the characteristics of the SEI layer formed at the anode surface. For example, a bicyclic sulfate-based compound comprising a sulfate group may accept electrons from the anode more readily than a polar solvent. For example, the biscyclosulfate-based compound may be reduced at a lower voltage than that required for the polar solvent reduction before the polar solvent is reduced.
For example, the bicyclic sulfate-based compounds include sulfate groups and thus may be more easily reduced and/or decomposed into free 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 a solvent. The bicyclic sulfate-based compound may form covalent bonds with, for example, the carbonaceous anode itself or various functional groups on the surface of the carbonaceous anode, or may be adsorbed onto the surface of the electrode. The modified SEI layer formed by such bonding and/or adsorption with improved stability can be more durable even after long-time charge and discharge, compared to an SEI layer formed only by an organic solvent. The durable modified SEI layer may instead more effectively prevent co-intercalation of organic solvents solvated lithium ions during lithium ion intercalation electrodes. Accordingly, the modified SEI layer may more effectively prevent direct contact between the organic solvent and the anode to further improve reversibility of intercalation/deintercalation of lithium ions, thereby achieving an increase in discharge capacity and an improvement in life characteristics of the fabricated battery.
In addition, since the sulfate group is included, the dicyclic sulfate-based compound may coordinate on the cathode surface, thereby affecting the characteristics of the protective layer formed on the cathode surface. For example, the sulfate group may coordinate with a transition metal ion of the cathode active material to form a complex. The complex can form a modified protective layer with improved stability, which is more durable than a protective layer formed of only an organic solvent even after long-time charge and discharge. In addition, the durable modified protective layer may more effectively prevent co-intercalation of organic solvents solvated lithium ions during intercalation of lithium ions into the electrode. Therefore, the modified protective layer can more effectively prevent direct contact between the organic solvent and the cathode to further improve reversibility of intercalation/deintercalation of lithium ions, thereby achieving improved stability and improved life characteristics of the fabricated battery.
Furthermore, the biscyclosulfate-based compound has a structure in which a plurality of rings are linked in a spiro form, and thus has a relatively larger molecular weight than the usual sulfate-based compound, and thus, may be thermally stable.
For example, the dicyclic sulfate-based compound may form an SEI layer at a protective layer of an anode surface or a cathode surface, and may exhibit enhanced lifetime characteristics of lithium batteries manufactured at high temperature due to improved thermal stability.
In the above-mentioned bicyclic sulfate-based compound of formula 1 contained in the organic electrolyte solution, A 1 、A 2 、A 3 And A 4 At least one of which may be unsubstituted or substituted C 1 -C 5 Alkylene, and substituted C 1 -C 5 The substituent of the alkylene group may be halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen substituted or unsubstituted C 3 -C 20 Heterocyclic ringSubstituted or unsubstituted C by radicals, halogen 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl or a polar functional group having at least one heteroatom.
For example, A 1 、A 2 、A 3 And A 4 At least one of which may be unsubstituted or substituted C 1 -C 5 Alkylene, and substituted C 1 -C 5 The substituent of the alkylene group may be halogen, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl. For example, the substituents of the substituted C1-C5 alkylene groups may be suitable substituents for the alkylene groups used in the art.
In some embodiments, in the bicyclic sulfate-based compounds of formula 1 above, the substituted C 1 -C 5 The substituent of the alkylene group may be a polar functional group having a heteroatom. The heteroatom of the polar functional group may be at least one selected from halogen, oxygen, nitrogen, phosphorus, sulfur, silicon and boron.
For example, the polar functional group having a heteroatom may be at least one selected from the group consisting of: -F, -Cl, -Br, -I, -C (=o) OR 16 、-OR 16 、-OC(＝O)OR 16 、-R 15 OC(＝O)OR 16 、-C(＝O)R 16 、-R 15 C(＝O)R 16 、-OC(＝O)R 16 、-R 15 OC(＝O)R 16 、-C(＝O)-O-C(＝O)R 16 、-R 15 C(＝O)-O-C(＝O)R 16 、-SR 16 、-R 15 SR 16 、-SSR 16 、-R 15 SSR 16 、-S(＝O)R 16 、-R 15 S(＝O)R 16 、-R 15 C(＝S)R 16 、-R 15 C(＝S)SR 16 、-R 15 SO 3 R 16 、-SO 3 R 16 、-NNC(＝S)R 16 、-R 15 NNC(＝S)R 16 、-R 15 N＝C＝S、-NCO、-R 15 -NCO、-NO 2 、-R 15 NO 2 、-R 15 SO 2 R 16 、-SO 2 R 16 、
In the above formula, R 11 And R is 15 May each independently be halogen substituted or unsubstituted C 1 -C 20 Alkylene, halogen substituted or unsubstituted C 2 -C 20 Alkenylene, halogen substituted or unsubstituted C 2 -C 20 Alkynylene, halogen substituted or unsubstituted C 3 -C 12 Cycloalkylene, halogen substituted or unsubstituted C 6 -C 40 Arylene, halogen substituted or unsubstituted C 2 -C 40 Heteroarylene, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl or halogen substituted or unsubstituted C 7 -C 15 Aralkylene radicals. R is R 12 、R 13 、R 14 And R is 16 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 12 Cycloalkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl, halogen substituted or unsubstituted C 7 -C 15 Trialkylsilyl or halogen substituted or unsubstituted C 7 -C 15 Aralkyl group, andrepresenting the binding site to an adjacent atom.
For example, in polar functional groups having heteroatoms, the halogen substituent of an alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkylaryl, trialkylsilyl or aralkyl group can be fluorine (F).
For example, the bicyclic sulfate-based compound contained in the organic electrolyte solution may be represented by formula 2 or 3:
wherein in formulas 2 and 3, B 1 、B 2 、B 3 、B 4 、D 1 And D 2 Can each independently be-C (E 1 )(E 2 ) -, carbonyl or sulfinyl. E (E) 1 And E is 2 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
For example, E 1 And E is 2 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 10 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
For example, E 1 And E is 2 Can each independently be hydrogen, F, chlorine (Cl), bromine (Br), iodine (I), methyl, ethyl, propyl, isopropyl, butyl, t-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl, or pyridyl.
For example, E 1 And E is 2 May each independently be hydrogen, F, methyl, ethyl, trifluoromethyl, tetrafluoroethyl or phenyl.
For example, the bicyclic sulfate-based compound may be represented by formula 4 or 5:
Wherein in formula 4 and formula 5, R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 May each independently be hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
For example, in the above formulas 4 and 5, R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 May each independently be hydrogen, F, cl, br, I, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
For example, in the above formulas 4 and 5, R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 May each independently be hydrogen, F, methyl, ethyl, propyl, trifluoromethyl, tetrafluoroethyl or phenyl.
For example, the bicyclic sulfate-based compound may be represented by one of the following formulas 6 to 17:
as used herein, the expression "C a -C b "a and b represent the number of carbon atoms of a particular functional group. For example, the functional group may include a to b carbon atoms. For example, the expression "C 1 -C 4 Alkyl "means an alkyl group having 1 to 4 carbon atoms, i.e. CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 CH 2 CH 2 CH 2 -、CH 3 CH 2 CH(CH 3 ) -and (CH) 3 ) 3 C-。
Depending on the context, a particular group may be referred to as a monovalent group or a divalent group. For example, a substituent may be understood as a divalent group when it requires two binding sites for binding to the rest of the molecule. For example, the substituents designated as alkyl groups requiring two binding sites may be divalent groups, e.g., -CH 2 -、-CH 2 CH 2 -、-CH 2 CH(CH 3 )CH 2 -and the like. The term "alkylene" as used herein means that the group is a divalent group.
The terms "alkyl" and "alkylene" as used herein refer to a branched or unbranched aliphatic hydrocarbon group. In one embodiment, the alkyl group may be substituted or unsubstituted. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl, wherein each of these groups may be optionally substituted or unsubstituted. In one embodiment, the alkyl group may have 1 to 6 carbon atoms. For example, C 1 -C 6 Alkyl groups can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, 3-pentyl, hexyl, and the like.
The term "cycloalkyl" as used herein refers to a fully saturated carbocyclic ring or ring system. For example, cycloalkyl groups may be cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The term "alkenyl" as used herein refers to a hydrocarbon group having 2 to 20 carbon atoms and having at least one carbon-carbon double bond. Examples of alkenyl groups include vinyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl. In one embodiment, these alkenyl groups may be substituted or unsubstituted. In one embodiment, alkenyl groups may have 2 to 40 carbon atoms.
The term "alkynyl" as used herein refers to a hydrocarbon group having 2 to 20 carbon atoms and having at least one carbon-carbon triple bond. Examples of alkynyl groups include ethynyl, 1-propynyl, 1-butynyl and 2-butynyl. In one embodiment, these alkynyl groups may be substituted or unsubstituted. In one embodiment, alkynyl groups may have 2 to 40 carbon atoms.
The term "aromatic" as used herein refers to a ring or ring system having a conjugated pi electron system, and may refer to carbocyclic aromatic groups (e.g., phenyl) and heterocyclic aromatic groups (e.g., pyridine). In this regard, the aromatic ring system as a whole may comprise a single ring or a fused multiple ring (i.e., rings sharing adjacent pairs of atoms).
The term "aryl" as used herein refers to an aromatic ring or ring system having only carbon atoms in its backbone (i.e., rings fused by at least two rings sharing two adjacent carbon atoms). When aryl is a ring system, each ring in the ring system is aromatic. Examples of aryl groups include phenyl, biphenyl, naphthyl, phenanthryl, and tetracenyl. These aryl groups may be substituted or unsubstituted.
The term "heteroaryl" as used herein refers to an aromatic ring system having one ring or multiple fused rings, wherein at least one ring atom is not carbon, i.e., a heteroatom. In a fused ring system, at least one heteroatom may be present in only one ring. For example, the heteroatom may be oxygen, sulfur or nitrogen. Examples of heteroaryl groups include furyl, thienyl, imidazolyl, quinazolinyl, quinolinyl, isoquinolinyl, quinoxalinyl, pyridyl, pyrrolyl, oxazolyl and indolyl.
The terms "aralkyl" and "alkylaryl" as used herein refer to an aryl group attached as a substituent through an alkylene group, e.g., C 7 -C 14 Aralkyl groups. Example packages of aralkyl or alkylaryl groupsIncluding benzyl, 2-phenylethyl, 3-phenylpropyl and naphthylalkyl. In one embodiment, the alkylene may be a lower alkylene (i.e., C 1 -C 4 An alkylene group).
The term "cycloalkenyl" as used herein refers to a non-aromatic carbocyclic ring or ring system having at least one double bond. For example, the cycloalkenyl group may be cyclohexenyl.
The term "heterocyclyl" as used herein refers to a non-aromatic ring or ring system having at least one heteroatom in its ring backbone.
The term "halogen" as used herein refers to a stable element belonging to group 17 of the periodic table of elements, such as fluorine, chlorine, bromine or iodine. For example, halogen may be fluorine and/or chlorine.
In this specification, a substituent may be obtained by substituting at least one hydrogen atom in an unsubstituted parent group with another atom or functional group. The term "substituted" means that the functional group listed above is substituted with at least one substituent selected from the group consisting of: c (C) 1 -C 40 Alkyl, C 2 -C 40 Alkenyl, C 3 -C 40 Cycloalkyl, C 3 -C 40 Cycloalkenyl and C 7 -C 40 Aryl groups. The phrase "optionally substituted" as used herein means that the above-described functional groups may be substituted with the above-described substituents or may be unsubstituted.
The amount of the bicyclic sulfate-based compound of formula 1 as an additive in the organic electrolyte solution may be in the range of about 0.4wt% to about 5wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 as an additive in the organic electrolyte solution may be in the range of about 0.4wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.6wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be about 0.7wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be about 0.4wt% to about 2.5wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be about 0.4wt% to about 2wt% based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be about 0.4wt% to about 1.5wt% based on the total weight of the organic electrolyte solution. When the amount of the biscyclosulfate based compound of formula 1 is within the above range, further enhanced battery characteristics can be obtained.
The first lithium salt included in the organic electrolyte solution may include at least one selected from the group consisting of: liPF (LiPF) 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiClO 4 、LiCF 3 SO 3 、Li(CF 3 SO 2 ) 2 N、LiC 4 F 9 SO 3 、LiAlO 2 、LiAlCl 4 、LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) (wherein x is more than or equal to 2 and less than or equal to 20, and y is more than or equal to 2 and less than or equal to 20), liCl and LiI.
The concentration of the first lithium salt in the organic electrolyte solution may be, for example, about 0.01M to about 2.0M. The concentration of the first lithium salt in the organic electrolyte solution may be appropriately adjusted as needed. When the concentration of the first lithium salt is within the above range, a battery having further enhanced characteristics can be obtained.
The organic solvent contained in the organic electrolyte solution may be a low boiling point solvent. The term "low boiling point 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), ethylmethyl carbonate (EMC), methylpropyl carbonate, ethylpropyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, propylene Carbonate (PC), ethylene Carbonate (EC), butylene carbonate, ethyl propionate, ethyl butyrate, acetonitrile, succinonitrile (SN), dimethyl sulfoxide, dimethylformamide, dimethylacetamide, gamma valerolactone, gamma butyrolactone and tetrahydrofuran. For example, the organic solvent may be a suitable solvent having a low boiling point available in the art.
In addition to the bicyclic sulfate-based compound, the organic electrolyte solution may further comprise other additives. By further including other additives, a lithium battery having further enhanced performance can be obtained.
Additives further included in the organic electrolyte solution may include cyclic carbonate compounds, second lithium salts, and the like.
For example, the organic electrolyte solution may further contain a cyclic carbonate compound as an additive. The cyclic carbonate compound used as an additive may be selected from Vinylene Carbonate (VC), selected from halogen, cyano (-CN) and nitro (-NO) 2 ) VC, vinyl Ethylene Carbonate (VEC), substituted by at least one substituent selected from the group consisting of halogen, -CN and-NO 2 VEC substituted by at least one substituent of (C); fluoroethylene carbonate (FEC) and one selected from halogen, -CN and-NO 2 FEC substituted by at least one substituent of (a). When the organic electrolyte solution further contains a cyclic carbonate compound as an additive, a lithium battery containing the organic electrolyte solution may have further enhanced charge and discharge characteristics.
The amount of cyclic carbonate compound in the organic electrolyte solution may be, for example, about 0.01wt% to about 5wt% based on the total weight of the organic electrolyte solution. The amount of the cyclic carbonate compound may be appropriately adjusted as needed. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.1wt% to about 5wt% based on the total weight of the organic electrolyte solution. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.1wt% to about 4wt% based on the total weight of the organic electrolyte solution. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.1wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.1wt% to about 2wt% based on the total weight of the organic electrolyte solution. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.2wt% to about 2wt% based on the total weight of the organic electrolyte solution. For example, the amount of cyclic carbonate compound in the organic electrolyte solution may be about 0.2wt% to about 1.5wt% based on the total weight of the organic electrolyte solution. When the amount of the cyclic carbonate compound is within the above range, a battery having further enhanced characteristics can be obtained.
For example, the organic electrolyte solution may further include a second lithium salt as an additive. The second lithium salt is distinct (i.e., different) from the first lithium salt. The anion of the second lithium salt can be oxalic acid radical, PO 2 F 2 - 、N(SO 2 F) 2 - Etc. For example, the second lithium salt may be a compound represented by one of the following formulas 18 to 25:
the amount of the second lithium salt in the organic electrolyte solution may be about 0.1wt% to about 5wt% based on the total weight of the organic electrolyte solution. The amount of the second lithium salt may be appropriately adjusted if necessary. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.1wt% to about 4.5wt% based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.1wt% to about 4wt% based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.1wt% to about 3wt% based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.1wt% to about 2wt% based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.2wt% to about 2wt% based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be about 0.2wt% to about 1.5wt% based on the total weight of the organic electrolyte solution. When the amount of the second lithium salt is within the above range, a battery having further enhanced characteristics can be obtained.
The organic electrolyte solution may be in a liquid or gel state. The organic electrolyte solution may be prepared by adding the above-described first lithium salt and an additive to the above-described organic solvent.
The nickel-containing layered lithium transition metal oxide contained in the cathode of the lithium battery may be represented by, for example, the following formula 26:
< 26>
Li a Ni x Co y M z O 2-b A b
Wherein in formula 26, a is 1.0.ltoreq.a.ltoreq.1.2, b is 0.ltoreq. 0.2,0.6.ltoreq.x <1,0< y is 0.2,0< z is 0.2, and x+y+z=1; m is at least one selected from manganese (Mn), vanadium (V), magnesium (Mg), gallium (Ga), silicon (Si), tungsten (W), molybdenum (Mo), iron (Fe), chromium (Cr), copper (Cu), zinc (Zn), titanium (Ti), aluminum (Al) and boron (B); and A is fluorine (F), sulfur (S), chlorine (Cl), bromine (Br), or a combination thereof. For example, 0.7.ltoreq.x <1,0< y.ltoreq.0.15, 0< z.ltoreq.0.15, and x+y+z=1. For example, 0.75.ltoreq.x <1,0< y.ltoreq.0.125, 0< z.ltoreq.0.125, and x+y+z=1. For example, 0.8.ltoreq.x <1,0< y.ltoreq.0.1, 0< z.ltoreq.0.1, and x+y+z=1. For example, 0.85.ltoreq.x <1,0< y.ltoreq.0.075, 0< z.ltoreq.0.075, and x+y+z=1.
The nickel-containing layered lithium transition metal oxide contained in the cathode of the lithium battery may be represented by, for example, formula 27 or formula 28:
< 27>
LiNi x Co y Mn z O 2
< 28>
LiNi x Co y Al z O 2
Wherein in the formulas 27 and 28, 0.6.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.2, 0< z.ltoreq.0.2, and x+y+z=1. For example, 0.7.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.15, 0< z.ltoreq.0.15, and x+y+z=1. For example, 0.75.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.125, 0< z.ltoreq.0.125, and x+y+z=1. For example, 0.8.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.1, 0< z.ltoreq.0.1, and x+y+z=1. For example, 0.85.ltoreq.x.ltoreq.0.95, 0< y.ltoreq.0.075, 0< z.ltoreq.0.075, and x+y+z=1.
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, a lithium battery may have a high voltage of about 3.80V or higher. For example, a lithium battery may have a high voltage of about 4.0V or higher. For example, a lithium battery may have a high voltage of about 4.35V or higher.
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 cathode active material, conductive material, binder, and solvent are mixed. The cathode active material composition may be directly coated onto a metal current collector, thereby completing the fabrication of a cathode plate. In some embodiments, the cathode active material composition may be cast onto a separate support, and a film separate from the support may be laminated onto the metal current collector, thereby completing the fabrication of the cathode plate.
For example, the cathode active material may be a compound represented by any one of the following formulas: li (Li) a A 1-b B' b D 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0 and less than or equal to 0.5; li (Li) a E 1-b B' b O 2-c D c Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05; liE 2-b B' b O 4-c D c Wherein b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05; li (Li) a Ni 1-b-c Co b B' c D α Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α≤2；Li a Ni 1-b-c Co b B' c O 2-α F' α Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；Li a Ni 1-b-c Co b B' c O 2-α F' 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；Li a Ni 1-b-c Mn b B' c D α Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α≤2；Li a Ni 1-b-c Mn b B' c O 2-α F' α Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；Li a Ni 1-b-c Mn b B' c O 2-α F' 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.05, and 0<α<2；Li a Ni b E c G d O 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, and d is more than or equal to 0.001 and less than or equal to 0.1; li (Li) a Ni b Co c Mn d G e O 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8,0, b is more than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, d is more than or equal to 0 and less than or equal to 0.5, and e is more than or equal to 0.001 and less than or equal to 0.1; li (Li) a NiG b O 2 Wherein 0.90.ltoreq.a.ltoreq.1.8 and 0.001.ltoreq.b.ltoreq.0.1; li (Li) a CoG b O 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.1; li (Li) a MnG b O 2 Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.1; li (Li) a Mn 2 G b O 4 Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.1; QO (quality of service) 2 ；QS 2 ；LiQS 2 ；V 2 O 5 ；LiV 2 O 5 ；LiI'O 2 ；LiNiVO 4 ；Li (3-f) J 2 (PO 4 ) 3 Wherein f is more than or equal to 0 and less than or equal to 2; li (Li) (3-f) Fe 2 (PO 4 ) 3 Wherein f is more than or equal to 0 and less than or equal to 2; liFePO 4 。
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 LiCoO 2 ；LiMn x O 2x Wherein x=1 or 2; liNi 1-x Mn x O 2x Wherein 0 is<x<1；LiNi 1-x-y Co x Mn y O 2 Wherein 0 is<1-x-y<0.6,0 x is less than or equal to 0.5, and y is less than or equal to 0 and less than or equal to 0.5; liFePO 4 Etc.
In addition, the above-mentioned lithium-containing metal oxide used as a cathode active material may have a coating layer on the surface thereof. In another embodiment, a mixture of a lithium-containing metal oxide and a lithium-containing metal oxide having a coating on its surface may be used. The coating may comprise a coating element compound, such as an oxide of a coating element, a hydroxide of a coating element, a oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element. The coating element compound may be amorphous or crystalline. The coating element included in the coating layer may be selected from Mg, al, co, potassium (K), sodium (Na), calcium (Ca), silicon (Si), ti, V, tin (Sn), germanium (Ge), gallium (Ga), boron (B), arsenic (As), zirconium (Zr), and mixtures thereof. The coating layer may be formed by using a suitable method (e.g., spraying, dipping, etc.) that does not adversely affect the physical properties of the cathode active material, by using the coating element in the above-mentioned compound.
Suitable conductive substances may be used. The conductive material may be, for example, carbon black, graphite particles, and the like.
The adhesive may be a suitable adhesive used in the art. Examples of binders include vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene, mixtures thereof, and styrene butadiene rubber based polymers.
The solvent may be, for example, N-methylpyrrolidone, acetone, water, etc.
The amounts of the cathode active material, the conductive material, the binder, and the solvent may be the same as those used in a general lithium battery. Depending on the intended use and configuration of the lithium battery, at least one of the conductive material, binder, and solvent may be omitted.
Anodes can be prepared by suitable manufacturing methods. 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 a film separate from the support may be laminated onto a metal current collector to complete the fabrication of the anode plate.
As the anode active material, a suitable anode active material for a lithium battery may be used. For example, the anode active material may include at least one selected from lithium metal, metal that can alloy with lithium, transition metal oxide, non-transition metal oxide, and carbonaceous material.
For example, the metal that can be alloyed with lithium may be Si, sn, al, ge, lead (Pb), bismuth (Bi), antimony (Sb), si-Y 'alloys (Y' is an alkali metal, alkaline earth metal, group 13 and 14 element, transition metal, rare earth element, or a combination thereof, and is not Si), sn-Y 'alloys (Y' is an alkali metal, alkaline earth metal, group 13 and 14 element, transition metal, rare earth element, or a combination thereof, and is not Sn), and the like. The element Y' may be selected from Mg, ca, sr, ba, radium (Ra), sc, Y, ti, zr, hafnium (Hf),(Rf), V, niobium (Nb), tantalum (Ta)>(Db), cr, mo, tungsten (W), and (B)>(Sg), technetium (Tc), rhenium (Re)>(Bh), fe, pb, ruthenium (Ru), osmium (Os), -, and the like>(Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), cu, silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), B, al, ga, sn, indium (In), ge, P, as, sb, bi, S, selenium (Se), tellurium (Te), polonium (Po), and combinations thereof.
For example, the transition metal oxide may be lithium titanium oxide, vanadium oxide, lithium vanadium oxide, or the like.
For example, the non-transition metal oxide may be SnO 2 、SiO x (wherein 0<x<2) Etc.
For example, the carbonaceous material may be crystalline carbon, amorphous carbon, or mixtures thereof. Examples of the crystalline carbon include natural graphite and artificial graphite, each of which has an irregular shape or is in the form of a plate, a sheet, a sphere, or a fiber. Examples of amorphous carbon include soft carbon (low temperature calcined carbon), hard carbon, mesophase pitch carbonized products, and calcined coke.
In the anode active material composition, the same conductive material and binder as those used in the cathode active material composition may be used.
The amounts of the anode active material, the conductive material, the binder, and the solvent may be the same as those used in a general lithium battery. Depending on the intended use and configuration of the lithium battery, at least one of the conductive material, binder, and solvent may be omitted.
A suitable separator to be disposed between the cathode and the anode may be prepared. As the separator, a separator having low resistance to ion migration in the electrolyte and having high electrolyte holding capacity can be used. Examples of separators may include fiberglass, polyester, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and combinations thereof, each of which may be a nonwoven or woven fabric. For example, a rollable separator formed of polyethylene, polypropylene, or the like may be used for a lithium ion battery, and a separator having a high organic electrolyte solution retaining ability may be used for a lithium ion polymer battery. For example, the separator may be manufactured according to the following method.
The polymer resin, filler, and solvent may be mixed together to prepare the separator composition. The separator composition may then be coated directly onto an electrode and dried to form a 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 to 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 vinylidene fluoride/hexafluoropropylene copolymer, PVDF, polyacrylonitrile, polymethyl methacrylate, mixtures thereof, and the like.
An 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, a 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 into a double battery structure and impregnated with an organic electrolyte solution, and the resultant may be put into a pouch and sealed, thereby completing the fabrication of a lithium battery.
The battery packs may be stacked to form a battery pack, and such battery packs may be used in devices requiring high capacity and high power output. For example, the battery pack may be used for a notebook computer, a smart phone, an electric vehicle, and the like.
The lithium battery may have excellent life characteristics and high rate characteristics, and thus may be used for an Electric Vehicle (EV). For example, lithium batteries may be used in hybrid vehicles, such as plug-in hybrid electric vehicles (PHEVs), and the like. Lithium batteries are also used in fields where a large amount of electricity needs to be stored. For example, lithium batteries may be used in electric bicycles, motor driven tools, and the like.
The following examples and comparative examples are provided to highlight features of one or more embodiments, but it should be understood that the examples and comparative examples should not be construed as limiting the scope of the embodiments nor as being outside the scope of the embodiments. Furthermore, it should be understood that the embodiments are not limited to the specific details described in the examples and comparative examples.
Synthesis of additives
Preparation example 1: synthesis of Compound of formula 6
The compound of formula 6 can be prepared according to the following reaction scheme 1:
< reaction scheme 1>
Synthesis of Compound A
68.0g (0.499 mol) of pentaerythritol and 100g of molecular sieve (type 4A) were added to a volume ratio of 1:1 of Tetrahydrofuran (THF) and dichloromethane (DCM, CH) 2 Cl 2 ) And the resulting solution was refluxed for 20 minutes. Subsequently, 110ml (2.8 eq, 1.40 mol) of thionyl chloride (SOCl) 2 ) To the resultant was added and the resulting solution was refluxed for 8 hours until pentaerythritol was completely consumed by the reaction, thereby obtaining a pale yellow solution. The resulting pale yellow solution was filtered and concentrated to give a residue containing a pale yellow solid. Thereafter, 1L of saturated sodium bicarbonate (NaHCO) 3 ) The solution is added directly to the residue at a rate that minimizes effervescence to give a suspension. The suspension was vigorously stirred for 20 minutes. Then, the suspension was filtered, and the resulting solid was added to 1L of purified water to prepare a mixture. The mixture was then vigorously stirred for 20 minutes, suction filtered, and dried in air, to give 104.61g (0.458 mol) of Compound A (yield: 92%).
Compound A 1 H-NMR 13 The C-NMR data are the same as in the literature.
Synthesis of Compound B
As shown in the above reaction scheme 1, compound B represented by the following formula 6 was synthesized from compound a according to the method disclosed in Canadian Journal of Chemistry,79,2001, page 1042.
The synthesized compound was recrystallized in a mixed solvent of 1, 2-dichloroethane and acetonitrile in a volume ratio of 2:1, and then used for preparing an electrolyte solution.
< 6>
Preparation of organic electrolyte solution
Example 1: SEI-1316.0 wt%
0.90M LiPF as lithium salt 6 And 1wt% of the compound of formula 6 was added to a mixed solvent of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) in a volume ratio of 3:5:2 to prepare an organic electrolyte solution.
< 6>
Example 2: SEI-1316.0wt% +VC 0.5wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that 1wt% of the compound of formula 6 and 0.5wt% of Vinylene Carbonate (VC) were used as additives.
Example 3: SEI-1316.5 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 0.5 wt%.
Example 4: SEI-1316.2 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-1316.3 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-1316.7 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-1316.5 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 1.5 wt%.
Example 8: SEI-1316 2wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 2 wt%.
Example 9: SEI-1316 3wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 3 wt%.
Example 9a: SEI-1316 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 4 wt%.
Example 10: SEI-1316 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 5 wt%.
Comparative example 1: SEI-1316 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the compound of formula 6 was not used as an additive.
Lithium battery production (examples 1-1 to 3-1 and comparative example 1-1)
Example 1-1
Manufacture of anode
98wt% of artificial graphite (BSG-L manufactured by Tianjin BTR New Energy Technology co., ltd.) as a binder, 1.0wt% of styrene-butadiene rubber (SBR) (manufactured by Zeon) and 1.0wt% of carboxymethyl cellulose (CMC) (manufactured by NIPPON a & L) were mixed together, the mixture was added to distilled water, and the resulting solution was stirred using a mechanical stirrer for 60 minutes to prepare an anode active material slurry. The anode active material slurry was coated onto a copper (Cu) current collector having a thickness of 10 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 ℃ for 0.5 hours, followed by further drying under the following conditions: the fabrication of the anode plate was completed by performing vacuum at 120 deg.c for 4 hours and rolling.
Cathode fabrication
97.45wt% of LiNi 1/3 Co 1/3 Mn 1/3 O 2 0.5wt% of powdered artificial graphite (SFG 6 manufactured by Timcal), 0.7wt% of carbon black (Ketjen black manufactured by ECP), 0.25wt% of modified acrylonitrile rubber (BM-720H manufactured by Zeon Corporation), 0.9wt% of polyvinylidene fluoride (PVDF, S6020 manufactured by Solvay) and 0.2wt% of PVDF (S5130 manufactured by Solvay) as a conductive substance were mixed together, and the mixture was added to N-methyl-2-pyrrolidone as a solvent, and the resulting solution was stirred using a mechanical stirrer for 30 minutes to prepare a cathode active material slurry. The cathode active material slurry was coated onto an aluminum (Al) current collector having a thickness of 20 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 ℃ for 0.5 hours, followed by further drying under the following conditions: the production of the cathode plate was completed by performing vacuum at 120℃for 4 hours and rolling.
A polyethylene separator (manufactured by SK Innovation) having a thickness of 14 μm was used, the cathode side of which was coated with ceramic, and the manufacture of a lithium battery was completed using the organic electrolyte solution prepared according to example 1.
Examples 2-1 and 3-1
A lithium battery was fabricated in the same manner as in example 1-1, except that the organic electrolyte solutions prepared according to examples 2 and 3 were used instead of the organic electrolyte solution of example 1, respectively.
Comparative example 1-1
A lithium battery was fabricated in the same manner as in example 1-1, except that the organic electrolyte solution prepared according to comparative example 1 was used instead of the organic electrolyte solution of example 1.
Evaluation example 1: evaluation of charge and discharge characteristics at 4.25V and at room temperature (25 ℃ C.)
The lithium batteries manufactured according to examples 1-1 to 3-1 and comparative example 1-1 were each charged at 25 ℃ with a constant current at 0.1C rate until the voltage reached 4.25V (relative to Li), and then the charging process was cut off with a current at 0.05C rate while maintaining a constant voltage of 4.25V. Subsequently, each lithium battery was discharged with a constant current of 0.1C magnification until the voltage reached 2.8V (with respect to Li) (forming operation, first cycle).
Each lithium battery after the first cycle of the forming operation was charged at 25 ℃ with a constant current of 0.2C rate until the voltage reached 4.25V (relative to Li), and then the charging process was cut off with a current of 0.05C rate while maintaining a constant voltage of 4.25V. Subsequently, each lithium battery was discharged with a constant current of 0.2C magnification until the voltage reached 2.8V (with respect to Li) (forming operation, second cycle).
Each lithium battery after the second cycle of the forming operation was charged at 25 ℃ with a constant current at a rate of 1.0C until the voltage reached 4.25V (relative to Li), and then the charging process was cut off with a current at a rate of 0.05C while maintaining a constant voltage of 4.25V. Subsequently, each lithium battery was discharged at a constant current of 1.0C magnification until the voltage reached 2.75V (with respect to Li), and the charge and discharge cycle was repeated 380 times.
In all charge and discharge cycles, there was a rest time of 10 minutes at the end of each charge/discharge cycle.
A part of the charge and discharge experimental results are shown in table 1 below and in fig. 1 and 2. The capacity retention rate of the 380 th cycle is defined using equation 1 below:
equation 1
Capacity retention = [ 380 th cycle discharge capacity/1 st cycle discharge capacity ] ×100
TABLE 1
Discharge capacity [ mAh/g of 380 th cycle] Capacity retention [%]
Example 1-1 202 75
Example 2-1 228 82
Comparative example 1-1 173 63
As shown in table 1 and fig. 1 and 2, the lithium batteries of examples 1-1 and 2-1, which included additives according to embodiments of the present disclosure, exhibited significantly enhanced discharge capacity and life characteristics at room temperature as compared to the lithium battery of comparative example 1-1, which did not include such additives.
Evaluation example 2: evaluation of charge and discharge characteristics at 4.25V and high temperature (45 ℃ C.)
The charge and discharge characteristics of the lithium batteries of examples 1-1 to 3-1 and comparative example 1-1 were evaluated using the same method as that used in evaluation example 1, except that the charge and discharge temperature was changed to 45 ℃. Meanwhile, the number of charge and discharge cycles was changed to 200 cycles.
A portion of the charge and discharge experimental results are shown in table 2 below and in fig. 3 and 4. The capacity retention rate of the 200 th cycle is defined using the following equation 2:
Equation 2
Capacity retention = [ discharge capacity at 200 th cycle/discharge capacity at 1 st cycle ] ×100
TABLE 2
Discharge capacity [ mAh/g of 200 th cycle] Capacity retention [%]
Example 1-1 249 83
Example 2-1 255 84
Comparative example 1-1 235 79
As shown in table 2 and fig. 3 and 4, the lithium batteries of examples 1-1 and 2-1 including the additive according to the embodiment of the present disclosure exhibited significantly enhanced discharge capacity and life characteristics at high temperature as compared to the lithium battery of comparative example 1-1 without such additive.
Evaluation example 3: evaluation of charge and discharge characteristics at 4.30V and at room temperature (25 ℃ C.)
The lithium batteries of example 1-1 and comparative example 1-1 were each charged at 25 ℃ with a constant current at 0.1C rate until the voltage reached 4.30V (relative to Li), and then the charging process was cut off with a current at 0.05C rate while maintaining a constant voltage of 4.30V. Subsequently, each lithium battery was discharged with a constant current of 0.1C magnification until the voltage reached 2.8V (with respect to Li) (forming operation, first cycle).
Each lithium battery after the first cycle of the forming operation was charged at 25 ℃ with a constant current of 0.2C rate until the voltage reached 4.30V (relative to Li), and then the charging process was cut off with a current of 0.05C rate while maintaining a constant voltage of 4.30V. Subsequently, each lithium battery was discharged with a constant current of 0.2C magnification until the voltage reached 2.8V (with respect to Li) (forming operation, second cycle).
Each lithium battery after the second cycle of the forming operation was charged at 25 ℃ with a constant current at 0.5C rate until the voltage reached 4.30V (relative to Li), and then the charging process was cut off with a current at 0.05C rate while maintaining a constant voltage of 4.30V. Subsequently, each lithium battery was discharged at a constant current of 1.0C magnification until the voltage reached 2.75V (with respect to Li), and the charge and discharge cycle was repeated 250 times.
In all charge and discharge cycles, there was a rest time of 10 minutes at the end of each charge/discharge cycle.
A part of the charge and discharge test results are shown in table 3 below and fig. 5. The capacity retention rate of the 250 th cycle is defined using the following equation 3:
equation 3
Capacity retention = [ discharge capacity of 250 th cycle/discharge capacity of 1 st cycle ] ×100
TABLE 3 Table 3
Discharge capacity [ mAh/g of 250 th cycle] Capacity retention [%]
Example 1-1 171 84
Comparative example 1-1 154 77
As shown in table 3 and fig. 5, the lithium battery of example 1-1 including the additive according to the embodiment of the present disclosure exhibited significantly enhanced discharge capacity and life characteristics at room temperature as compared to the lithium battery of comparative example 1-1 not including such additive.
Evaluation example 4: evaluation of charge and discharge characteristics at 4.30V and high temperature (45 ℃ C.)
The charge and discharge characteristics of the lithium batteries of example 1-1 and comparative example 1-1 were evaluated using the same method as that used in evaluation example 3, except that the charge and discharge temperature was changed to 45 ℃. And, the number of charge and discharge cycles was changed to 200 cycles.
A part of the charge and discharge test results are shown in table 4 below and fig. 6. The capacity retention rate of the 200 th cycle is defined using the following equation 4:
equation 4
Capacity retention = [ discharge capacity at 200 th cycle/discharge capacity at 1 st cycle ] ×100
TABLE 4 Table 4
Discharge capacity [ mAh/g of 200 th cycle] Capacity retention [%]
Example 1-1 189 90
Comparative example 1-1 174 84
As shown in table 4 and fig. 6, the lithium battery of example 1-1 including the additive according to the embodiment of the present disclosure exhibited significantly enhanced discharge capacity and life characteristics at high temperature as compared to the lithium battery of comparative example 1-1 not including such additive.
Evaluation example 5: evaluation of high temperature (60 ℃ C.) stability
The lithium batteries of examples 1-1 to 3-1 and comparative example 1-1 were subjected to first charge and discharge cycles as follows. Each lithium battery was charged at 25C with a constant current of 0.5C rate until the voltage reached 4.3V, then, while maintaining a constant voltage of 4.3V, each lithium battery was charged until the current reached 0.05C, and then discharged with a constant current of 0.5C rate until the voltage reached 2.8V.
Each lithium battery was subjected to a second charge and discharge cycle as follows. Each lithium battery was charged with a constant current of 0.5C rate until the voltage reached 4.3V, then, each lithium battery was charged until the current reached 0.05C while maintaining a constant voltage of 4.3V, and then discharged with a constant current of 0.2C rate until the voltage reached 2.8V.
A third charge and discharge cycle was performed for each lithium battery as follows. Each lithium battery was charged with a constant current of 0.5C rate until the voltage reached 4.3V, then, each lithium battery was charged until the current reached 0.05C while maintaining a constant voltage of 4.3V, and then discharged with a constant current of 0.2C rate until the voltage reached 2.80V. The discharge capacity at the 3 rd cycle was regarded as the standard capacity.
A fourth charge and discharge cycle was performed for each lithium battery as follows. Each lithium battery was charged at 0.5C rate until the voltage reached 4.30V, then, each lithium battery was charged until the current reached 0.05C while maintaining a constant voltage of 4.30V, the charged battery was stored in an oven at 60℃ for 10 days and 30 days, then, the battery was taken out of the oven, and then discharged at 0.1C rate until the voltage reached 2.80V.
A part of the charge and discharge evaluation results are shown in table 5 below. The capacity retention after high temperature storage is defined using the following equation 5:
equation 5
Capacity retention after high temperature storage [% ] = [ high temperature discharge capacity at 4 th cycle/standard capacity ] ×100 (herein, standard capacity is discharge capacity at 3 rd cycle)
TABLE 5
As shown in table 5, the lithium battery of example 3-1 including the organic electrolyte solution according to the embodiment of the present disclosure exhibited significantly enhanced high temperature stability compared to the lithium battery of comparative example 1-1 not including the organic electrolyte solution of the present invention.
Evaluation example 6: evaluation of direct-current internal resistance (DC-IR) after high-temperature (60 ℃ C.) storage
DC-IR of each lithium battery of examples 1-1 to 3-1 and comparative example 1-1 was measured at room temperature (25 ℃) before being placed in an oven at 60 ℃, after being stored in an oven at 60 ℃ for 10 days, and after being stored in an oven at 60 ℃ for 30 days, using the following methods.
Each lithium battery was subjected to a first charge and discharge cycle as follows. Each lithium battery was charged at a current of 0.5C until the voltage reached 50% soc (state of charge), the charging process was cut off at 0.02C, and then each lithium battery was left to stand for 10 minutes. Subsequently, the following treatments were performed for each lithium battery: discharging for 30 seconds at a constant current of 0.5C, then standing for 30 seconds, and charging for 30 seconds at a constant current of 0.5C, then standing for 10 minutes; discharging for 30 minutes at a constant current of 1.0C, then standing for 30 seconds, and charging for 1 minute at a constant current of 0.5C, then standing for 10 minutes; discharging for 30 seconds at a constant current of 2.0C, then standing for 30 seconds, and charging for 2 minutes at a constant current of 0.5C, then standing for 10 minutes; discharging for 30 seconds at a constant current of 3.0C, then standing for 30 seconds, and charging for 2 minutes at a constant current of 0.5C, then standing for 10 minutes.
The average voltage reduction value of 30 seconds at each C-ratio is a dc voltage value.
A portion of the increase in the dc internal resistance calculated from the measured initial dc internal resistance and the dc internal resistance after high temperature storage is shown in table 6 below. The dc internal resistance increase is represented by the following equation 6:
equation 6
The increase of the internal resistance of the direct current [% ] = [ internal resistance of the direct current after high-temperature storage/initial internal resistance of the direct current ] x100
TABLE 6
As shown in table 6, the lithium battery of example 3-1 including the organic electrolyte solution according to the embodiment of the present disclosure showed a decrease in the increase in the direct current internal resistance after high-temperature storage, compared to the lithium battery of comparative example 1-1 not including the organic electrolyte solution.
Lithium battery production (examples A1 to A11, reference examples A1 to A5, and comparative examples A1 to A3)
Example A1: NCM, ni60+ SEI-1316.5 wt%
Manufacture of anode
98wt% of artificial graphite (BSG-L manufactured by Tianjin BTR New Energy Technology co., ltd.) and 1.0wt% of SBR (manufactured by Zeon) as a binder and 1.0wt% of CMC (manufactured by NIPPON a & L) were mixed together, the mixture was added to distilled water, and the resulting solution was stirred using a mechanical stirrer for 60 minutes to prepare an anode active material slurry. The anode active material slurry was coated onto a Cu current collector having a thickness of 10 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 ℃ for 0.5 hours, then further dried in vacuo at 120 ℃ for 4 hours, and roll-pressed, thereby completing the fabrication of an anode plate.
Cathode fabrication
97.45wt% of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 0.5wt% of powdered artificial graphite (SFG 6 manufactured by Timcal), 0.7wt% of carbon black (Ketjen black manufactured by ECP), 0.25wt% of modified acrylonitrile rubber (BM-720H manufactured by Zeon corporation), 0.9wt% of PVDF (S6020 manufactured by Solvay) and 0.2wt% of PVDF (S5130 manufactured by Solvay) as a conductive substance were mixed together, and the mixture was added to N-methyl-2-pyrrolidone as a solvent, and the resulting solution was stirred 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 hours, then further vacuum-dried at 120 ℃ for 4 hours, and roll-pressed, thereby completing the fabrication of a cathode plate.
The manufacture of a lithium battery was completed using a polyethylene separator having a thickness of 14 μm and a cathode side coated with ceramic and an organic electrolyte solution prepared according to example 3.
Example A2: NCM, ni60+ SEI-1316.7wt%
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 A3: NCM, ni60+ SEI-1316 1wt%
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 A4: NCM, ni60+ SEI-1316.5 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 A5: NCM, ni60+ SEI-1316 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 A6: NCM, ni88+ SEI-1316 1wt%
In addition to using Li 1.02 Ni 0.88 Co 0.08 Mn 0.04 O 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example A1, except that the electrolyte solution of example 1 was used as the cathode active material.
Example A7: NCA, ni88+ SEI-1316.5wt%
In addition to using Li 1.02 Ni 0.88 Co 0.08 Al 0.04 O 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example A1, except that a cathode active material was used.
Example A8: NCA, ni88+ SEI-1316.7wt%
In addition to using Li 1.02 Ni 0.88 Co 0.08 Al 0.04 O 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example A1, except that the electrolyte solution of example 6 was used as the cathode active material.
Example A9: NCA, ni88+ SEI-1316 1wt%
In addition to using Li 1.02 Ni 0.88 Co 0.08 Al 0.04 O 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example A1, except that the electrolyte solution of example 1 was used as the cathode active material.
Example a10: NCA, ni88+ SEI-1316 wt%
In addition to using Li 1.02 Ni 0.88 Co 0.08 Al 0.04 O 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 As a cathode active material, and an electrolyte solution prepared according to example 9 was used as an electrolyte solution, a lithium battery was fabricated in the same manner as in example A1.
Example a11: NCA, ni91+SEI-1316 1wt%
In addition to using Li 1.02 Ni 0.91 Co 0.05 Al 0.04 O 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example A1, except that the electrolyte solution of example 1 was used as the cathode active material.
Reference example A1: ni55+SEI-1316 1wt%
In addition to using Li 1.02 Ni 0.55 Co 0.25 Mn 0.20 O 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example A1, except that the electrolyte solution of example 1 was used as the cathode active material.
Reference example A2: NCM, ni60+ SEI-1316.2wt%
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 A3: NCM, ni60+ SEI-1316 5wt%
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 A4: NCA, ni88+ SEI-1316.2wt%
In addition to using Li 1.02 Ni 0.88 Co 0.08 Al 0.04 O 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 As a cathode active material, and 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 instead of the organic electrolyte solution of example 3.
Reference example A5: NCA, ni88+ SEI-1316 5wt%
In addition to using Li 1.02 Ni 0.88 Co 0.08 Al 0.04 O 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example A1, except that the electrolyte solution of example 10 was used as a cathode active material instead of the organic electrolyte solution of example 3.
Comparative example A1: ni60+SEI-13160wt%
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 A2: LCO, ni00+SEI-1316 wt%
In addition to using LiCoO 2 Substitution of Li 1.02 Ni 0.60 Co 0.20 Mn 0.20 O 2 A lithium battery was fabricated in the same manner as in example A1, except that the organic electrolytic solution of example 1 was used as the cathode active material, as well as that of the electrolyte solution.
Comparative example A3: NCM+LMO+SEI-1316 1wt%
Except that LiNi was used in a weight ratio of 1:1 1/3 Co 1/3 Mn 1/3 O 2 And LiMn 2 O 4 Is a mixture of (2) instead of Li 1.02 Ni 0.85 Co 0.10 Mn 0.05 O 2 A lithium battery was fabricated in the same manner as in example A1, except that the organic electrolytic solution of example 1 was used as the cathode active material, as well as that of the electrolyte solution.
Evaluation example A1: evaluation of charge/discharge characteristics at 4.25V and at room temperature (25 ℃ C.)
The charge/discharge characteristics of the lithium batteries manufactured according to examples A1 to a11, reference examples A1 to A5, and comparative examples A1 to A3 were evaluated using the same method as that used in evaluation example 1.
A part of the charge and discharge test results are shown in table A1 below. The capacity retention rate of the 380 th cycle is defined using equation 1 below:
equation 1
Capacity retention = [ 380 th cycle discharge capacity/1 st cycle discharge capacity ] ×100
Table A1
As shown in table A1, the lithium batteries of examples A1 to a11 of the present disclosure, which contain additives and have a high nickel content, exhibited significantly enhanced lifetime characteristics at room temperature, as compared to the lithium batteries of comparative examples A1 to A3, which contain cathode active materials having a low nickel content or no additives.
Further, the lithium batteries of examples A1 to a11 each containing a certain amount of additive exhibited more enhanced life characteristics at room temperature as compared with the lithium batteries of reference examples A2 to A5 each containing an amount of additive outside a certain range.
Evaluation example A2: evaluation of direct current-internal resistance (DC-IR) after high temperature (60 ℃ C.) storage
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 DC-IR increase 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
The increase of the internal resistance of the direct current [% ] = [ the internal resistance of the direct current after high-temperature storage/the initial internal resistance of the direct current ] ×100
Table A2
As shown in table A2, the lithium batteries of examples A1 to a11 of the present disclosure, which included additives and cathode active materials having a high nickel content, exhibited lower DC-IR increases than each of the lithium batteries of comparative examples A1 to A3, which included cathode active materials having a low nickel content and no additives.
Furthermore, the lithium batteries of examples A1 to a11 containing a certain amount of additive exhibited lower DC-IR increase than each of the lithium batteries of reference examples A1 to A5 containing an amount of additive outside a certain range.
As apparent from the foregoing description, a lithium battery including a cathode having a lithium transition metal oxide with a high nickel content and an organic electrolyte solution containing a novel bicyclosulfate-based additive can exhibit enhanced high temperature characteristics and life characteristics.
By way of summary and review, aqueous electrolyte solutions that are highly reactive to lithium may not be suitable for use in lithium batteries when such batteries are operated at high operating voltages. Lithium batteries typically use organic electrolyte solutions. The organic electrolyte solution is prepared by dissolving a lithium salt in an organic solvent. An organic solvent having stability at a high voltage, high ionic conductivity, high dielectric constant and low viscosity may be used.
When a lithium battery uses a general organic electrolyte solution including a carbonate-based polar nonaqueous solvent, irreversible reaction of excessive use of charges due to side reactions between an anode/cathode and the organic electrolyte solution may occur during initial charge. Due to such irreversible reaction, a passivation layer, such as a Solid Electrolyte Interface (SEI) layer, may be formed on the surface of the anode. In addition, a protective layer is formed on the surface of the cathode.
In this regard, the SEI layer and/or the protective layer formed using the existing organic electrolyte solution may be easily degraded. For example, such an SEI layer and/or protective layer may exhibit reduced stability at high temperatures.
Accordingly, an organic electrolyte solution capable of forming an SEI layer and/or a protective layer having improved high temperature stability is desired.
Various embodiments of the present 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 lifetime characteristics.
Exemplary embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purpose of limitation. In some cases, it will be apparent to one of ordinary skill in the art at the time of filing this application that features, characteristics, and/or elements described in connection with particular embodiments may be used alone or in combination with features, characteristics, and/or elements described in connection with other embodiments unless explicitly stated otherwise. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope thereof as set forth in the appended claims.

Claims (17)

1. A lithium battery, comprising:
a cathode including a cathode active material;
an anode comprising an anode active material; and
an organic electrolyte solution between the cathode and the anode,
wherein the cathode active material comprises a nickel-containing layered lithium transition metal oxide, the nickel content in the lithium transition metal oxide being 60mol% or more relative to the total 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:
< 1>
Wherein in formula 1, A 1 、A 2 、A 3 And A 4 Each independently is a covalent bond, substituted or unsubstituted C 1 -C 5 Alkylene, carbonyl or sulfinyl, wherein A 1 And A 2 Not all are covalent bonds, and A 3 And A 4 Not all of them are covalent bonds and,
wherein the lithium transition metal oxide is represented by the following formula 26:
< 26>
Li a Ni x Co y M z O 2-b A b
Wherein in formula 26, 1.0.ltoreq.a.ltoreq.1.2, 0.ltoreq.b.ltoreq. 0.2,0.85 < x <1,0< y.ltoreq.0.075, 0< z.ltoreq.0.075, and x+y+z=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;
a is fluorine, chlorine, bromine or a combination thereof; and is also provided with
Wherein the amount of the bicyclic sulfate based compound is greater than 0.5wt% to less than 5wt% based on the total weight of the organic electrolyte solution.
2. As claimed inThe lithium battery of claim 1, wherein A 1 、A 2 、A 3 And A 4 At least one of which is unsubstituted or substituted C 1 -C 5 Alkylene group, wherein the substituted C 1 -C 5 The substituent of the alkylene group is at least one selected from the following: halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen-substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl, halogen substituted or unsubstituted C 2 -C 40 Heteroaryl or a polar functional group having at least one heteroatom.
3. The lithium battery of claim 1, wherein a 1 、A 2 、A 3 And A 4 At least one of which is unsubstituted or substituted C 1 -C 5 Alkylene group, wherein the substituted C 1 -C 5 The substituent of the alkylene group is halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
4. The lithium battery of claim 2, wherein the substituted C 1 -C 5 The substituent of the alkylene group includes the polar functional group having at least one heteroatom, wherein the polar functional group is at least one selected from the group consisting of: -F, -Cl, -Br, -I, -C (=o) OR 16 、-OR 16 、-OC(＝O)OR 16 、-R 15 OC(＝O)OR 16 、-C(＝O)R 16 、-R 15 C(＝O)R 16 、-OC(＝O)R 16 、-R 15 OC(＝O)R 16 、-C(＝O)-O-C(＝O)R 16 、-R 15 C(＝O)-O-C(＝O)R 16 、-SR 16 、-R 15 SR 16 、-SSR 16 、-R 15 SSR 16 、-S(＝O)R 16 、-R 15 S(＝O)R 16 、-R 15 C(＝S)R 16 、-R 15 C(＝S)SR 16 、-R 15 SO 3 R 16 、-SO 3 R 16 、-NNC(＝S)R 16 、-R 15 NNC(＝S)R 16 、-R 15 N＝C＝S、-NCO、-R 15 -NCO、-NO 2 、-R 15 NO 2 、-R 15 SO 2 R 16 、-SO 2 R 16 、
Wherein, in the above formula, R 11 And R is 15 Each independently is halogen substituted or unsubstituted C 1 -C 20 Alkylene, halogen substituted or unsubstituted C 2 -C 20 Alkenylene, halogen substituted or unsubstituted C 2 -C 20 Alkynylene, halogen substituted or unsubstituted C 3 -C 12 Cycloalkylene, halogen substituted or unsubstituted C 6 -C 40 Arylene, halogen substituted or unsubstituted C 2 -C 40 Heteroarylene, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl or halogen substituted or unsubstituted C 7 -C 15 An aralkylene group; and is also provided with
R 12 、R 13 、R 14 And R is 16 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 12 Cycloalkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl groupHalogen substituted or unsubstituted C 2 -C 40 Heteroaryl, halogen substituted or unsubstituted C 7 -C 15 Alkylaryl, halogen substituted or unsubstituted C 7 -C 15 Trialkylsilyl or halogen substituted or unsubstituted C 7 -C 15 Aralkyl groups.
5. The lithium battery of claim 1, wherein the bicyclic sulfate-based compound is represented by formula 2 or formula 3:
wherein in formula 2 and formula 3, B 1 、B 2 、B 3 、B 4 、D 1 And D 2 Each independently is-C (E) 1 )(E 2 ) -carbonyl or sulfinyl; and is also provided with
E 1 And E is 2 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 2 -C 20 Alkenyl, halogen substituted or unsubstituted C 2 -C 20 Alkynyl, halogen substituted or unsubstituted C 3 -C 20 Cycloalkenyl, halogen substituted or unsubstituted C 3 -C 20 Heterocyclyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
6. The lithium battery of claim 5, wherein E 1 And E is 2 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 10 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
7. The lithium battery of claim 5, wherein E 1 And E is 2 Each independently is hydrogenFluorine, 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:
wherein in formula 4 and formula 5, R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 Each independently is hydrogen, halogen substituted or unsubstituted C 1 -C 20 Alkyl, halogen substituted or unsubstituted C 6 -C 40 Aryl or halogen substituted or unsubstituted C 2 -C 40 Heteroaryl groups.
9. The lithium battery of claim 8, wherein R 1 、R 2 、R 3 、R 4 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 And R is 28 Each independently is hydrogen, F, cl, br, I, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl, or pyridinyl.
10. The lithium battery of claim 1, wherein the bicyclic sulfate-based compound is represented by one of the following formulas 6 to 17:
11. the lithium battery of claim 1, wherein the amount of the bicyclosulfate-based compound is greater than 0.5wt% to 3wt%, based on the total weight of the organic electrolyte solution.
12. The lithium battery of claim 1, wherein the first lithium salt in the organic electrolyte solution comprises at least one selected from the group consisting of: liPF (LiPF) 6 、LiBF 4 、LiSbF 6 、LiAsF 6 、LiClO 4 、LiCF 3 SO 3 、Li(CF 3 SO 2 ) 2 N、LiC 4 F 9 SO 3 、LiAlO 2 、LiAlCl 4 、LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ) (wherein x is more than or equal to 2 and less than or equal to 20, and y is more than or equal to 2 and less than or equal to 20), liCl and LiI.
13. The lithium battery of claim 1, wherein the organic electrolyte solution further comprises a cyclic carbonate compound, wherein the cyclic carbonate compound is selected from the group consisting of vinylene carbonate, vinylene carbonate substituted with at least one substituent selected from the group consisting of halogen, cyano and nitro, fluoroethylene carbonate, and fluoroethylene carbonate substituted with at least one substituent selected from the group consisting of halogen, cyano and nitro.
14. The lithium battery of claim 13, wherein the amount of the cyclic carbonate compound is 0.01wt% to 5wt%, based on the total weight of the organic electrolyte solution.
15. The lithium battery of claim 1, wherein the organic electrolyte solution further comprises a second lithium salt, the second lithium salt being different from the first lithium salt and represented by one of the following formulas 18-25:
16. the lithium battery of claim 15, wherein the amount of the second lithium salt is 0.1wt% to 5wt%, based on the total weight of the organic electrolyte solution.
17. The lithium battery of claim 1, wherein the lithium transition metal oxide is a compound represented by the following formula 27 or formula 28:
< 27>
LiNi x Co y Mn z O 2
< 28>
LiNi x Co y Al z O 2
Wherein in formulas 27 and 28, 0.85< x.ltoreq.0.95, 0< y.ltoreq.0.075, 0< z.ltoreq.0.075, and x+y+z=1.
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