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CN110931855A - Lithium battery - Google Patents

Lithium battery Download PDF

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Publication number
CN110931855A
CN110931855A CN201910360134.7A CN201910360134A CN110931855A CN 110931855 A CN110931855 A CN 110931855A CN 201910360134 A CN201910360134 A CN 201910360134A CN 110931855 A CN110931855 A CN 110931855A
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unsubstituted
halogen substituted
lithium battery
substituted
electrolyte solution
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罗哈娜
金暻洙
金允熙
金载弘
柳洙烈
孙美暎
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 US16/135,349 external-priority patent/US11251432B2/en
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Priority to KR1020190114965A priority Critical patent/KR20200033203A/en
Publication of CN110931855A publication Critical patent/CN110931855A/en
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    • 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
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Abstract

The lithium battery includes a cathode including a cathode active material; an anode including an anode active material; and an organic electrolyte solution between the cathode and the anode, wherein the anode active material includes artificial graphite and natural graphite, an amount of the artificial graphite is about 50 wt% or more based on the total weight of the anode active material, and the organic electrolyte solution includes: a first lithium salt, an organic solvent; and a bicyclic sulfate-based compound represented by the following formula 1:<formula 1>
Figure DDA0002046587440000011
Wherein, in formula 1, A1、A2、A3And A4Each independently a covalent bond, substituted or unsubstituted C1‑C5Alkylene, carbonyl or sulfinyl, in which A1And A2Not all being covalent bonds and A3And A4Not all covalent bonds.

Description

Lithium battery
Cross Reference to Related Applications
The present application claims the benefit of U.S. patent application serial No. 15/422,873 entitled "lithium battery" filed 2018, 9, 19, continues to No. 16/135,349, which is incorporated herein by reference in its entirety.
Technical Field
One or more embodiments relate to a lithium battery.
Background
Lithium batteries are used as driving power sources for portable electronic devices including video cameras, mobile phones, notebook computers, and the like. The lithium secondary battery is rechargeable at a high speed and has an energy density per unit weight at least three times as large as that of an existing lead storage battery, nickel-cadmium battery, nickel-hydrogen battery or nickel-zinc battery.
Disclosure of Invention
Embodiments relate to a lithium battery including: a cathode including a cathode active material; an anode including an anode active material; and an organic electrolyte solution between the cathode and the anode. The anode active material includes natural graphite and artificial graphite in an amount of about 50 wt% or more based on the total weight of the anode active material. The organic electrolyte solution includes a first lithium salt, an organic solvent, and a bicyclic sulfate-based compound represented by formula 1 below:
< formula 1>
Figure BDA0002046587420000011
Wherein, in formula 1, A1、A2、A3And A4Each independently a covalent bond, substituted or unsubstituted C1-C5Alkylene, carbonyl or sulfinyl, in which A1And A2Not all being covalent bonds and A3And A4Not all covalent bonds.
A1、A2、A3And A4At least one of which may be unsubstituted or substituted C1-C5Alkylene, wherein said substituted C1-C5The substituent of the alkylene is selected fromAt least one of: halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen substituted or unsubstituted C3-C20Heterocyclyl, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl or a polar functional group having at least one heteroatom.
A1、A2、A3And A4At least one of which may be unsubstituted or substituted C1-C5Alkylene, wherein said substituted C1-C5The substituent of the alkylene group is halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
Said substituted C1-C5The substituent of alkylene may include the polar functional group having at least one hetero atom, wherein the polar functional group is at least one selected from the group consisting of: -F, -Cl, -Br, -I, -C (═ O) OR16、-OR16、-OC(＝O)OR16、-R15OC(＝O)OR16、-C(＝O)R16、-R15C(＝O)R16、-OC(＝O)R16、-R15OC(＝O)R16、-C(＝O)-O-C(＝O)R16、-R15C(＝O)-O-C(＝O)R16、-SR16、-R15SR16、-SSR16、-R15SSR16、-S(＝O)R16、-R15S(＝O)R16、-R15C(＝S)R16、-R15C(＝S)SR16、-R15SO3R16、-SO3R16、-NNC(＝S)R16、-R15NNC(＝S)R16、-R15N＝C＝S、-NCO、-R15-NCO、-NO2、-R15NO2、-R15SO2R16、-SO2R16、
Figure BDA0002046587420000021
Figure BDA0002046587420000022
Figure BDA0002046587420000031
Wherein, in the above formula, R11And R15Each independently halogen substituted or unsubstituted C1-C20Alkylene, halogen substituted or unsubstituted C2-C20Alkenylene, halogen substituted or unsubstituted C2-C20Alkynylene, halogen substituted or unsubstituted C3-C12Cycloalkylene, halogen substituted or unsubstituted C6-C40Arylene, halogen substituted or unsubstituted C2-C40Heteroarylene, halogen substituted or unsubstituted C7-C15Alkylarylene or halogen substituted or unsubstituted C7-C15An aralkylene group; and R is12、R13、R14And R16Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C12Cycloalkyl, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl, halogen substituted or unsubstituted C7-C15Alkylaryl, halogen substituted or unsubstituted C7-C15Trialkylsilyl or halogen substituted or unsubstituted C7-C15Aralkyl, and
Figure BDA0002046587420000032
indicates and is adjacent toThe position of the atomic bonding.
The bicyclic sulfate-based compound may be represented by formula 2 or 3:
Figure BDA0002046587420000033
wherein, in formulae 2 and 3, B1、B2、B3、B4、D1And D2Each independently is-C (E)1)(E2) -, carbonyl or sulfinyl; and is
E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen substituted or unsubstituted C3-C20Heterocyclyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C10Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
E1And E2Each independently can be hydrogen, fluorine (F), chlorine (Cl), bromine (Br), iodine (I), methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridinyl.
The bicyclic sulfate-based compound may be represented by formula 4 or 5:
Figure BDA0002046587420000034
Figure BDA0002046587420000041
wherein, in formulae 4 and 5, R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently can be hydrogen, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
The bicyclic sulfate-based compound may be represented by one of the following formulas 6 to 17:
Figure BDA0002046587420000042
Figure BDA0002046587420000051
the amount of the bicyclic sulfate-based compound may be about 0.4 wt% to about 5 wt% based on the total weight of the organic electrolyte solution.
The amount of the bicyclic sulfate-based compound may be about 0.4 wt% to about 3 wt% based on the total weight of the organic electrolyte solution.
The first lithium salt in the organic electrolyte solution may include at least one selected from the group consisting of: LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiCF3SO3、Li(CF3SO2)2N、LiC4F9SO3、LiAlO2、LiAlCl4、LiN(CxF2x+1SO2)(CyF2y+1SO2) Wherein x is more than or equal to 2 and less than or equal to 20 and y is more than or equal to 2 and less than or equal to 20, LiCl and LiI.
The organic electrolyte solution may further include a cyclic carbonate compound. The cyclic carbonate compound may be selected from Vinylene Carbonate (VC); is selected from halogen, cyano (-CN) and nitro (-NO)2) VC substituted with at least one substituent of (a); vinyl Ethylene Carbonate (VEC); selected from halogen, -CN and-NO2VEC substituted with at least one substituent of (1); fluoroethylene carbonate (FEC); and is selected from halogen, -CN and-NO2FEC substituted with at least one substituent of (a).
The amount of the cyclic carbonate compound may be about 0.01 wt% to about 5 wt% based on the total weight of the organic electrolyte solution.
The organic electrolyte solution may further include a second lithium salt different from the first lithium salt and represented by one of the following formulae 18 to 25:
Figure BDA0002046587420000052
Figure BDA0002046587420000061
the amount of the second lithium salt may be about 0.1 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution.
The amount of natural graphite may be in the range of about 25 wt% to about 50 wt% based on the total weight of the anode active material.
The cathode may include a layered lithium transition metal oxide containing nickel.
The lithium battery may have a voltage of about 3.8V or more.
Drawings
Features will become apparent to those skilled in the art by describing in detail exemplary embodiments with reference to the attached drawings, wherein:
FIG. 1 illustrates 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 illustrates 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 illustrates graphs showing discharge capacities at high temperatures of lithium batteries of examples 1-1 and 2-1 and comparative example 1-1;
FIG. 4 illustrates graphs showing capacity retention rates at high temperatures of lithium batteries of examples 1-1 and 2-1 and comparative example 1-1;
FIG. 5 illustrates graphs showing capacity retention rates at room temperature of lithium batteries of example 1-1 and comparative example 1-1;
FIG. 6 illustrates graphs showing capacity retention rates at high temperatures of lithium batteries of example 1-1 and comparative example 1-1; and
fig. 7 illustrates a view of a lithium battery according to an embodiment.
Detailed Description
Exemplary embodiments will be described more fully hereinafter with reference to the accompanying drawings
The lithium battery according to the embodiment may include: a cathode including a cathode active material; an anode including an anode active material; and an organic electrolyte solution between the cathode and the anode. The anode active material may include natural graphite and artificial graphite. The amount of the artificial graphite may be about 50 wt% or more based on the total weight of the anode active material. The organic electrolyte solution may include a first lithium salt, an organic solvent, and a bicyclic sulfate-based compound represented by formula 1 below:
< formula 1>
Figure BDA0002046587420000071
Wherein, in formula 1, A1、A2、A3And A4Each independently a covalent bond, substituted or unsubstituted C1-C5Alkylene, carbonyl or sulfinyl, in which A1And A2Not all being covalent bonds and A3And A4Not all covalent bonds.
The organic electrolyte solution includes a bicyclic sulfate-based compound as an additive for a lithium battery, which can enhance battery performance, such as high temperature characteristics and life characteristics
In addition, when the anode includes natural graphite and artificial graphite as the anode active material, the amount of the artificial graphite is about 50 wt% or more and the amount of the natural graphite is about 25 wt% to about 50 wt% based on the total weight of the anode active material, the life characteristic and high temperature stability of the lithium battery may be further enhanced.
In a lithium battery including only natural graphite as an anode active material, life characteristics of the lithium battery may be significantly deteriorated due to side reactions. In contrast, in a lithium battery including an organic electrolyte solution and including artificial graphite in an amount of about 50 wt% or more and natural graphite in an amount of about 25 wt% to about 50 wt% based on the total weight of an anode active material, a rigid solid electrolyte membrane is formed on the surface of the natural graphite, and thus deterioration of life characteristics of the lithium battery due to side reactions can be effectively suppressed. In particular, the high temperature life characteristics and high temperature stability of the lithium battery can be further enhanced.
The bicyclic sulfate-based compound may have a structure in which two sulfate rings are connected to each other in a spiro form.
Without being bound by any particular theory and for a better understanding, the reason why the performance of the lithium battery can be improved by adding the bicyclic sulfate-based compound to the electrolyte solution will now be described in more detail.
The sulfate group of the bicyclic sulfate-based compound may be reduced by itself during charging by accepting electrons from the surface of the anode, or may react with a previously reduced polar solvent molecule, thereby affecting the characteristics of an SEI layer formed on the surface of the anode. For example, bicyclic sulfate-based compounds including a sulfate group may more readily accept electrons from the anode than polar solvents. For example, bicyclic sulfate-based compounds can be reduced at a lower voltage than that required to reduce a polar solvent before the polar solvent is reduced.
For example, bicyclic sulfate-based compounds include sulfate groups and thus may be more readily reduced and/or decomposed into radicals and/or ions during charging. Thus, radicals and/or ions are combined with lithium ions to form an appropriate SEI layer on the anode, thereby preventing formation of a product obtained by further decomposing the solvent. The bicyclic sulfate-based compound may form a covalent bond with various functional groups on, for example, the carbon-containing anode itself or the surface of the carbon-containing anode, or may adsorb on the surface of the electrode. The modified SEI layer having improved stability formed by such bonding and/or adsorption may be more durable than an SEI layer formed only of an organic solvent, even after being charged and discharged for a long period of time. The permanently modified SEI layer may in turn be more effective in blocking co-intercalation of lithium ions solvated by organic solvents during intercalation of lithium ions into the electrode. Accordingly, the modified SEI layer may more effectively block direct contact between the organic solvent and the anode to further improve reversibility of intercalation/deintercalation of lithium ions, so that discharge capacity is increased and life characteristics of the manufactured battery are improved.
Also, since a sulfate group is included, the bicyclic sulfate-based compound may coordinate on the surface of the cathode, thereby affecting the characteristics of the protective layer formed on the surface of the cathode. For example, the sulfate group may coordinate with a transition metal ion of the cathode active material to form a complex. The complex can form a modified protective layer with improved stability, which is more durable than a protective layer formed only of an organic solvent, even after charging and discharging for a long period of time. In addition, the durable modified protective layer can more effectively block co-intercalation of lithium ions solvated by an organic solvent during intercalation of the lithium ions into the electrode. Therefore, the modified protective layer can more effectively block direct contact between the organic solvent and the cathode to further improve the reversibility of intercalation/deintercalation of lithium ions, resulting in increased stability and improved life characteristics of the fabricated battery.
In addition, the bicyclic sulfate-based compound has a structure in which a plurality of rings are connected in a spiro form. Accordingly, bicyclic sulfate-based compounds may have a relatively larger molecular weight than general sulfate-based compounds, and thus, may be thermally stable.
For example, the bicyclic sulfate-based compound may form an SEI layer on the surface of an anode or a protective layer on the surface of a cathode and may exhibit enhanced life characteristics of a manufactured lithium battery at high temperature due to improved thermal stability.
In the bicyclic sulfate-based compound of formula 1 above, which is included in the organic electrolyte solution, A1、A2、A3And A4At least one of which may be unsubstituted or substituted C1-C5Alkylene, and substituted C1-C5The substituent of the alkylene group may be a halogen-substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen substituted or unsubstituted C3-C20Heterocyclyl, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl or a polar functional group having at least one heteroatom.
For example, A1、A2、A3And A4At least one of which may be unsubstituted or substituted C1-C5Alkylene, and substituted C1-C5The substituent for the alkylene group may be halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl. For example, substituted C1-C5The substituent of the alkylene group may be any suitable substituent used in the art for alkylene groups.
For example, in the bicyclic sulfate-based compound of formula 1 above, substituted C1-C5The substituent of the alkylene group may be a polar functional group having a hetero atom, and the hetero atom of the polar functional group may be selected from halogen, oxygen, nitrogenAt least one of 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) OR16、-OR16、-OC(＝O)OR16、-R15OC(＝O)OR16、-C(＝O)R16、-R15C(＝O)R16、-OC(＝O)R16、-R15OC(＝O)R16、-C(＝O)-O-C(＝O)R16、-R15C(＝O)-O-C(＝O)R16、-SR16、-R15SR16、-SSR16、-R15SSR16、-S(＝O)R16、-R15S(＝O)R16、-R15C(＝S)R16、-R15C(＝S)SR16、-R15SO3R16、-SO3R16、-NNC(＝S)R16、-R15NNC(＝S)R16、-R15N＝C＝S、-NCO、-R15-NCO、-NO2、-R15NO2、-R15SO2R16、-SO2R16、
Figure BDA0002046587420000091
Figure BDA0002046587420000092
Figure BDA0002046587420000101
In the above formula, R11And R15Each independently may be halogen substituted or unsubstituted C1-C20Alkylene, halogen substituted or unsubstituted C2-C20Alkenylene, halogen substituted or unsubstituted C2-C20Alkynylene, halogen substituted or unsubstituted C3-C12Cycloalkylene, halogen substituted or unsubstituted C6-C40Arylene, halogen substituted or unsubstituted C2-C40HeteroarylenesHalogen substituted or unsubstituted C7-C15Alkylarylene or halogen substituted or unsubstituted C7-C15An aralkylene group; and R is12、R13、R14And R16Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C12Cycloalkyl, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl, halogen substituted or unsubstituted C7-C15Alkylaryl, halogen substituted or unsubstituted C7-C15Trialkylsilyl or halogen substituted or unsubstituted C7-C15Aralkyl, and
Figure BDA0002046587420000102
indicates the position of bonding to the adjacent atom.
For example, in the polar functional group having a hetero atom, the halogen substituent of the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, heteroaryl group, alkylaryl group, trialkylsilyl group or arylalkyl group may be fluorine (F).
For example, the bicyclic sulfate-based compound included in the organic electrolyte solution may be represented by formula 2 or 3:
Figure BDA0002046587420000103
wherein, in formulae 2 and 3, B1、B2、B3、B4、D1And D2Each independently may be-C (E)1)(E2) -, carbonyl or sulfinyl; and E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogenSubstituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen substituted or unsubstituted C3-C20Heterocyclyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
E.g. E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C10Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
E.g. E1And E2Each independently can be hydrogen, F, chlorine (Cl), bromine (Br), iodine (I), methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridinyl.
E.g. E1And E2Each independently can be hydrogen, F, methyl, ethyl, trifluoromethyl, tetrafluoroethyl, or phenyl.
For example, bicyclic sulfate-based compounds may be represented by formula 4 or 5:
Figure BDA0002046587420000111
wherein, in formulae 4 and 5, R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
For example, in the above formulas 4 and 5, R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently can be hydrogen, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
For example, in the above formulas 4 and 5, R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently can be hydrogen, F, methyl, ethyl, propyl, trifluoromethyl, tetrafluoroethyl, or phenyl.
For example, the bicyclic sulfate-based compound may be represented by one of formulae 6 to 17:
Figure BDA0002046587420000112
Figure BDA0002046587420000121
as used herein, the expression "Ca-Cb"a and b" represent the number of carbon atoms of the specific functional group. For example, the functional group may include a to b carbon atoms. For example, the expression "C1-C4Alkyl "means an alkyl group having 1 to 4 carbon atoms, i.e., CH3-、CH3CH2-、CH3CH2CH2-、(CH3)2CH-、CH3CH2CH2CH2-、CH3CH2CH(CH3) -and (CH)3)3C-。
The specific group may be referred to as a monovalent group or a divalent group depending on the context. For example, when a substituent requires two binding sites for binding to the remaining molecule, the substituent may be understood as a divalent group. For example, a substituent specified as an alkyl requiring two binding sites may be a divalent group, such as-CH2-、-CH2CH2-or-CH2CH(CH3)CH2-and the like. The term "alkylene" as used herein expressly indicates that the group is a divalent group.
The terms "alkyl" and "alkylene" as used herein refer to branched or unbranched aliphatic hydrocarbon groups. In one embodiment, an alkyl group may be substituted or unsubstituted. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl, each of which may be optionally substituted or unsubstituted. In one embodiment, the alkyl group may have 1 to 6 carbon atoms. E.g. C1-C6The alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, 3-pentyl, hexyl or the like.
The term "cycloalkyl" as used herein refers to a fully saturated carbocyclic cyclic ring or ring system. For example, cycloalkyl groups can be cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
The term "alkenyl" as used herein refers to a hydrocarbon group having 2 to 20 carbon atoms and at least one carbon-carbon double bond. Examples of alkenyl groups include ethenyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl. In one embodiment, these alkenyl groups may be substituted or unsubstituted. In some embodiments, the alkenyl group can have 2 to 40 carbon atoms.
The term "alkynyl" as used herein refers to a hydrocarbyl group having 2 to 20 carbon atoms and at least one carbon-carbon triple bond. Examples of alkynyl groups include ethynyl, 1-propynyl, 1-butynyl and 2-butynyl. In one embodiment, these alkynyl groups may be substituted or unsubstituted. In one embodiment, the alkynyl group may have 2 to 40 carbon atoms.
The term "aromatic" as used herein refers to rings or ring systems having conjugated pi-electron systems, and may refer to carbocyclic aromatic groups (e.g., phenyl) and heterocyclic aromatic groups (e.g., pyridine). In this regard, the aromatic ring system as a whole may include a monocyclic ring or a fused polycyclic ring (i.e., rings that share 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., a ring fused by at least two rings sharing two adjacent carbon atoms). When the aryl group is a ring system, each ring in the ring system is aromatic. Examples of aryl groups include phenyl, biphenyl, naphthyl, phenanthryl, and tetracenyl. These aryl groups may be substituted or unsubstituted.
The term "heteroaryl" as used herein refers to an aromatic ring system having one ring or multiple fused rings, wherein at least one ring atom is not carbon, i.e., a heteroatom. In fused ring systems, at least one heteroatom may be present in only one ring. For example, the heteroatom may be oxygen, sulfur, or nitrogen. Examples of heteroaryl groups include furyl, thienyl, imidazolyl, quinazolinyl, quinolyl, isoquinolyl, quinoxalyl, 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, such as C7-C14An aralkyl group. Examples of aralkyl or alkylaryl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and naphthylalkyl. In one embodiment, the alkylene group may be a lower alkylene group (i.e., C)1-C4Alkylene).
The term "cycloalkenyl" as used herein refers to a non-aromatic carbocyclic ring or ring system having at least one double bond. For example, the cycloalkenyl group can be cyclohexenyl.
The term "heterocyclyl" as used herein refers to a non-aromatic ring or ring system having at least one heteroatom in its ring backbone.
The term "halogen" as used herein refers to a stabilizing element belonging to group 17 of the periodic table, for example, fluorine, chlorine, bromine or iodine. For example, the halogen may be fluorine and/or chlorine.
In the present specification, a substituent may be obtained by substituting at least one hydrogen atom in an unsubstituted parent group with another atom or functional group. Unless otherwise indicated, the term "substituted" means that the functional groups listed above are selected from at least one ofSubstituted by one substituent: c1-C40Alkyl radical, C2-C40Alkenyl radical, C3-C40Cycloalkyl radical, C3-C40Cycloalkenyl radical and C7-C40And (4) an aryl group. The phrase "optionally substituted" as used herein means that the above functional groups may be substituted with the above substituents.
The amount of the bicyclic sulfate-based compound of formula 1 as an additive in the organic electrolyte solution may range from about 0.4 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.5 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.6 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.7 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.4 wt% to about 4.5 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.4 wt% to about 4 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.4 wt% to about 3.5 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the bicyclic sulfate-based compound of formula 1 in the organic electrolyte solution may be in the range of about 0.4 wt% to about 3.0 wt%, based on the total weight of the organic electrolyte solution. When the amount of the bicyclic sulfate-based compound of formula 1 is within the above range, further enhanced battery characteristics may be obtained.
The first lithium salt included in the organic electrolyte solution may include at least one selected from the group consisting of: LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiCF3SO3、Li(CF3SO2)2N、LiC4F9SO3、LiAlO2、LiAlCl4、LiN(CxF2x+1SO2)(CyF2y+1SO2) Wherein x is more than or equal to 2 and less than or equal to 20 and y is more than or equal to 2 and less than or equal to 20, LiCl and LiI.
The concentration of the first lithium salt in the organic electrolyte solution may be, for example, about 0.01M to about 2.0M. The concentration of the first lithium salt in the organic electrolyte solution may be appropriately adjusted as necessary. When the concentration of the first lithium salt is within the above range, a battery having further enhanced characteristics may be obtained.
The organic solvent included 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 ℃ under 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.
The organic solvent may be a suitable solvent having a low boiling point. For example, the organic solvent may include at least one selected from the group consisting of: dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), propyl methyl carbonate, propyl ethyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, Propylene Carbonate (PC), Ethylene Carbonate (EC), butylene carbonate, ethyl propionate, ethyl butyrate, acetonitrile, Succinonitrile (SN), dimethyl sulfoxide, dimethylformamide, dimethylacetamide, γ -valerolactone, γ -butyrolactone, and tetrahydrofuran. For example, the organic solvent may be any suitable solvent having a low boiling point that is useful in the art.
In addition to the bicyclic sulfate-based compound, the organic electrolyte solution may further include other additives. By further including other additives, a lithium battery having further enhanced performance can be obtained.
The additive further included in the organic electrolyte solution may include a cyclic carbonate compound or a second lithium salt, etc.
For example, the organic electrolyte solution may further include a cyclic carbonate compoundAs an additive. The cyclic carbonate compound used as an additive may be selected from: vinylene Carbonate (VC); is selected from halogen, cyano (-CN) and nitro (-NO)2) VC substituted with at least one substituent of (a); vinyl Ethylene Carbonate (VEC); selected from halogen, -CN and-NO2VEC substituted with at least one substituent of (1); fluoroethylene carbonate (FEC); and is selected from halogen, -CN and-NO2FEC substituted with at least one substituent of (a). When the organic electrolyte solution further includes a cyclic carbonate compound as an additive, the lithium battery including the organic electrolyte solution may have further enhanced charge and discharge characteristics.
The amount of the cyclic carbonate compound in the organic electrolyte solution may be, for example, in the range of about 0.01 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution. The amount of the cyclic carbonate compound can be appropriately adjusted as necessary. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be in the range of about 0.1 wt% to about 5 wt% based on the total weight of the organic electrolyte solution. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be in the range of about 0.1 wt% to about 4 wt% based on the total weight of the organic electrolyte solution. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be in the range of about 0.1 wt% to about 3 wt% of nickel based on the total weight of the organic electrolyte solution. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be in the range of about 0.1 wt% to about 2 wt% based on the total weight of the organic electrolyte solution. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be in the range of about 0.2 wt% to about 2 wt% based on the total weight of the organic electrolyte solution. For example, the amount of the cyclic carbonate compound in the organic electrolyte solution may be about 0.2 wt% to about 1.5 wt% based on the total weight of the organic electrolyte solution. When the amount of the cyclic carbonate compound is within the above range, a battery having further enhanced characteristics may be obtained.
For example, the organic electrolyte solution may further include a second lithium salt as an additive, the second lithium salt being distinct (i.e., different) from the first lithium salt. The anion of the second lithium salt may be oxalate or PO2F2-or N (SO)2F)2-and the like. For example, the second lithium salt may be a compound represented by one of the following formulae 18 to 25:
Figure BDA0002046587420000161
the amount of the second lithium salt in the organic electrolyte solution may be in the range of about 0.1 wt% to about 5 wt%, based on the total weight of the organic electrolyte solution. The amount of the second lithium salt may be appropriately adjusted as needed. For example, the amount of the second lithium salt in the organic electrolyte solution may be in the range of about 0.1 wt% to about 4.5 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be in the range of about 0.1 wt% to about 4 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be in the range of about 0.1 wt% to about 3 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be in the range of about 0.1 wt% to about 2 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be in the range of about 0.2 wt% to about 2 wt%, based on the total weight of the organic electrolyte solution. For example, the amount of the second lithium salt in the organic electrolyte solution may be in the range of about 0.2 wt% to about 1.5 wt%, based on the total weight of the organic electrolyte solution. When the amount of the second lithium salt is within the above range, a battery having further enhanced characteristics may be obtained.
The organic electrolyte solution may be in a liquid state or a gel state. The organic electrolyte solution may be prepared by adding the above-described first lithium salt and an additive to the above-described organic solvent.
In a lithium battery, the anode may include natural graphite and artificial graphite. The amount of the artificial graphite may be about 50% or more with respect to the total weight of the anode active material. When the amount of the artificial graphite is within the above range, the life characteristics and high temperature stability of the lithium battery may be further enhanced. The amount of the natural graphite may be about 25% to about 50% with respect to the total weight of the anode active material.
The lithium battery may be, for example, a lithium ion battery, a lithium ion polymer battery, a lithium sulfur battery, or the like, or a lithium primary battery.
For example, in a lithium battery, the anode may comprise graphite. For example, in a lithium battery, the cathode may include a layered lithium transition metal oxide containing nickel. For example, lithium batteries may have a high voltage of about 3.80V or higher. For example, lithium batteries may have a high voltage of about 4.0V or higher. For example, lithium batteries may have a high voltage of about 4.35V or higher.
For example, a lithium battery can be manufactured using the following method.
The cathode can be prepared by a suitable manufacturing method. For example, a cathode active material composition in which a cathode active material, a conductive material, a binder, and a solvent are mixed may be prepared. The cathode active material composition may be directly coated on a metal current collector, thereby completing the manufacture of a cathode plate. In one embodiment, the cathode active material composition may be cast on a separate support and a membrane separate from the support may be laminated to a metal current collector, thereby completing the manufacture of the cathode plate.
The cathode active material may be a lithium-containing metal oxide. For example, the lithium-containing metal oxide may be at least one selected from the group consisting of: a composite oxide of lithium and a metal selected from the group consisting of cobalt, manganese, nickel, and combinations thereof. For example, the cathode active material may be a compound represented by any one of the following formulae: liaA1-bB'bD2Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0 and less than or equal to 0.5; liaE1-bB'bO2-cDcWherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05; LiE2-bB'bO4-cDcWherein b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.05; liaNi1-b-cCobB'cDαWherein a is 0.90-1.8, b is 0-0.5, c is 0-0.05, and<α≤2；LiaNi1-b- cCobB'cO2-αF'αwherein a is 0.90-1.8, b is 0-0.5, c is 0-0.05, and<α<2；LiaNi1-b-cCobB'cO2-αF'2wherein a is 0.90-1.8, b is 0-0.5, c is 0-0.05, and<α<2；LiaNi1-b-cMnbB'cDαwherein a is 0.90-1.8, b is 0-0.5, c is 0-0.05, and<α≤2；LiaNi1-b-cMnbB'cO2-αF'αwherein a is 0.90-1.8, b is 0-0.5, c is 0-0.05, and<α<2；LiaNi1-b-cMnbB'cO2-αF'2wherein a is 0.90-1.8, b is 0-0.5, c is 0-0.05, and<α<2；LiaNibEcGdO2wherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, and d is more than or equal to 0.001 and less than or equal to 0.1; liaNibCocMndGeO2Wherein a is more than or equal to 0.90 and less than or equal to 1.8, b is more than or equal to 0 and less than or equal to 0.9, c is more than or equal to 0 and less than or equal to 0.5, d is more than or equal to 0 and less than or equal to 0.5, and e is more than or equal to 0.001 and less than or equal to 0.1; liaNiGbO2Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.1; liaCoGbO2Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.1; liaMnGbO2Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.1; liaMn2GbO4Wherein a is more than or equal to 0.90 and less than or equal to 1.8, and b is more than or equal to 0.001 and less than or equal to 0.1; QO2；QS2；LiQS2；V2O5；LiV2O5；LiI'O2；LiNiVO4；Li(3-f)J2(PO4)3Wherein f is more than or equal to 0 and less than or equal to 2; li(3-f)Fe2(PO4)3Wherein f is more than or equal to 0 and less than or equal to 2; and LiFePO4。
In the above formula, A may be selected from nickel (Ni), cobalt (Co), manganese (Mn), and combinations thereof; b' may be selected from aluminum (Al), Ni, Co, manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), rare earth elements, and combinations thereof; d may be selected from oxygen (O), fluorine (F), sulfur (S), phosphorus (P), and combinations thereof; e may be selected from Co, Mn, and combinations thereof; f' may be selected from F, S, P and combinations thereof; g may be selected from Al, Cr, Mn, Fe, Mg, lanthanum (La), cerium (Ce), Sr, V, and combinations thereof; q may be selected from titanium (Ti), molybdenum (Mo), Mn, and combinations thereof; i' may be selected from Cr, V, Fe, scandium (Sc), yttrium (Y), and combinations thereof; and J may be selected from V, Cr, Mn, Co, Ni, copper (Cu), and combinations thereof.
For example, the cathode active material may be LiCoO2、LiMnxO2xWhere x is 1 or 2, LiNi1-xMnxO2xWherein 0<x<1、LiNi1-x-yCoxMnyO2Wherein x is more than or equal to 0 and less than or equal to 0.5 and y is more than or equal to 0 and less than or equal to 0.5 or LiFePO4And the like.
In addition, the lithium-containing metal oxides used as the cathode active material described above may have a coating layer on their surface. In another embodiment, lithium-containing metal oxides and mixtures of lithium-containing metal oxides with coating layers on the surfaces thereof can be used. The coating layer can include a coating element compound, such as an oxide of the coating element, a hydroxide of the coating element, a oxyhydroxide of the coating element, an oxycarbonate of the coating element, or a hydroxycarbonate of the coating element. The coating element compound may be amorphous or crystalline. The coating elements 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 the coating elements among the above-mentioned compounds by using any one of various methods (e.g., spraying or dipping, etc.) that do not adversely affect the physical properties of the cathode active material.
Suitable conductive materials may be used. For example, the conductive material may be carbon black or graphite particles, or the like.
A suitable adhesive may be used. Examples of binders include vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene, mixtures thereof, and styrene butadiene rubber-based polymers.
Suitable solvents may be used. The solvent may be, for example, N-methylpyrrolidone, acetone, or water.
The amounts of the cathode active material, the conductive material, the binder and the solvent may be the same levels as those used in a general lithium battery. At least one of a conductive material, a binder and a solvent may not be used according to the intended use and composition of the lithium battery.
The anode can be prepared by an appropriate manufacturing method. For example, the anode active material composition may be prepared by mixing an anode active material, a conductive material, a binder, and a solvent. The anode active material composition may be directly coated on a metal current collector and dried to obtain an anode plate. In another embodiment, the anode active material composition may be cast on a separate support and the membrane separate from the support may be laminated on the metal current collector to complete the fabrication of the anode plate.
The anode active material includes natural graphite having an irregular shape or a plate shape, a flake shape, a sphere shape, or a fiber shape, and may further include artificial graphite having an irregular shape or a plate shape, a flake shape, a sphere shape, or a fiber shape. In addition, an anode active material of a lithium battery used in the art may be further used. For example, the anode active material may include at least one selected from the group consisting of lithium metal, a metal that can be alloyed with lithium, a transition metal oxide, a non-transition metal oxide, and a carbonaceous material.
For example, the metal that can be alloyed with lithium can be Si, Sn, Al, Ge, lead (Pb), bismuth (Bi), antimony (Sb), Si-Y 'alloys (Y' is an alkali metal other than Si, an alkaline earth metal, group 13 and group 14 elements, a transition metal, a rare earth element, or a combination thereof) or Sn-Y 'alloys (Y' is an alkali metal other than Sn, an alkaline earth metal, group 13 and group 14 elements, a transition metal, a rare earth element, or a combination thereof), and the like. The element Y' is selected from Mg, Ca, Sr, barium (Ba), radium (Ra), Sc, Y, Ti, Zr, hafnium (Hf),
Figure BDA0002046587420000191
(Rf), V, niobium (Nb), tantalum (Ta),
Figure BDA0002046587420000192
(Db), Cr, Mo, tungsten (W),
Figure BDA0002046587420000193
(Sg), technetium (Tc), rhenium (Re),
Figure BDA0002046587420000194
(Bh), Fe, Pb, ruthenium (Ru), osmium (Os),
Figure BDA0002046587420000195
(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, or lithium vanadium oxide, or the like.
For example, the non-transition metal oxide can be SnO2、SiOxWherein 0<x<2, etc.
For example, the carbon-containing material may be crystalline carbon, amorphous carbon, or a mixture thereof. The crystalline carbon may be graphite. Examples of amorphous carbon include soft carbon (low temperature calcined carbon), hard carbon, products of mesophase pitch carbonization, and calcined coke.
In the anode active material composition, the same conductive materials and binders 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 levels as those used in a general lithium battery. At least one of the conductive material, the binder and the solvent may be omitted depending on the intended use and composition of the lithium battery.
A suitable separator may be prepared and disposed between the cathode and the anode.
As the separator, a separator having low resistance to ions in the transfer electrolyte and having high electrolyte retaining ability may be used. Examples of separators may include fiberglass, polyester, polyethylene, polypropylene, Polytetrafluoroethylene (PTFE), and combinations thereof, each of which may be a nonwoven or a woven fabric. For example, a windable separator formed of polyethylene, polypropylene, or the like may be used in a lithium ion battery, and a separator having a high organic electrolyte solution retaining ability may be used in 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 a separator composition. The separator composition can then be coated directly on the electrode and dried to form the separator. In another embodiment, the separator composition may be cast on the support and dried, and then, the separator film separated from the support may be laminated on the upper portion of the electrode, thereby completing the manufacture of the separator.
The polymer resin used to manufacture the separator may include suitable materials for the binder of the electrode plate. For example, the polymer resin may be a vinylidene fluoride/hexafluoropropylene copolymer, PVDF, polyacrylonitrile, polymethyl methacrylate, or a mixture thereof, or the like.
The organic electrolyte solution as described above may be prepared.
As illustrated in fig. 7, the lithium battery 1 includes a cathode 3, an anode 2, and a separator 4. The cathode 3, the anode 2 and the separator 4 are wound or folded and then placed in the battery case 5. Subsequently, an organic electrolyte solution is injected into the battery case 5, and the battery case 5 is sealed with the cap assembly 6, thereby completing the manufacture of the lithium battery 1. The battery case 5 may have a cylindrical, rectangular, or film shape.
A separator 4 may be disposed between the cathode 3 and the anode 2 to form a battery assembly. A plurality of battery modules may be stacked in a bicell structure and impregnated with an organic electrolyte solution, and the resultant is put in a pouch and sealed, thereby completing the manufacture of a lithium battery.
The battery pack may be stacked to form a battery pack, and the battery pack may be used for any device requiring high capacity and high power output. For example, the battery pack may be used for a notebook computer, a smart phone, an electric car, or the like.
Lithium batteries have excellent life characteristics and high rate characteristics and thus are useful for Electric Vehicles (EVs). For example, the lithium battery may be used for a hybrid vehicle such as a plug-in hybrid electric vehicle (PHEV) or the like. Lithium batteries are also used in locations where large amounts of electrical energy need to be stored. For example, lithium batteries may be used in electric bicycles or motor-driven tools, etc.
The following examples and comparative examples are provided to emphasize features of one or more embodiments, but it should be understood that examples and comparative examples are not to be construed as limiting the scope of the embodiments, nor are comparative examples to be construed as exceeding the scope of the embodiments. Further, it is understood that the embodiments are not limited to the specific details described in the examples and comparative examples.
Synthesis of additives
Preparation example 1: synthesis of Compounds of formula 6
The compound of formula 6 may be prepared according to the following reaction scheme 1:
< reaction scheme 1>
Figure BDA0002046587420000211
Synthesis of Compound A
68.0g (0.499mol) of pentaerythritol and 100g of molecular sieve (type 4A) are added to a volume ratio of 1:1 of Tetrahydrofuran (THF) and dichloromethane (DCM, CH)2Cl2) And the resulting solution was refluxed for 20 minutes. Subsequently, 110ml (2.8 eq, 1.40mol) of thionyl chloride (SOCl)2) Added to the resultant and the resultant solution was refluxed for 8 hours until all of the pentaerythritol was consumed by the reaction to obtain a pale yellow solution. The obtained light yellow solution was filtered and concentrated to obtain a residue comprising light yellow solids. Thereafter, 1L of saturated sodium bicarbonate (NaHCO)3) The solution was added directly to the residue at a rate that minimized bubbling to obtain a suspension. The suspension was stirred vigorously for 20 minutes. Thereafter, the suspension was filtered and the obtained solid was added to 1L of purified water to prepare a mixture. Then, the mixture was vigorously stirred for 20 minutes, suction-filtered, and dried in the air to obtain 104.61g (0.458mol) of Compound A (yield: 92%).
Of Compound A1H-NMR and13the C-NMR data are identical to those 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, which was then used to prepare an electrolyte solution.
< formula 6>
Figure BDA0002046587420000212
Preparation of organic electrolyte solution
Example 1: SEI-13161.0 wt.%
0.90M LiPF as lithium salt6And 1 wt% of the compound of formula 6 was added to a mixed solvent of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) in a volume ratio of 3:5:2 to prepare an organic electrolyte solution.
< formula 6>
Figure BDA0002046587420000221
Example 2: SEI-13161.0 wt% + VC 0.5 wt%
An organic electrolyte solution was prepared in the same manner as in example 1, except that 1 wt% of the compound of formula 6 and 0.5 wt% of Vinylene Carbonate (VC) were used as additives.
Example 3: SEI-13160.5 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 0.5 wt%.
Example 4: SEI-13160.2 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 0.2 wt%.
Example 5: SEI-13160.3 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 0.3 wt%.
Example 6: SEI-13160.7 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 0.7 wt%.
Example 7: SEI-13161.5 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 1.5 wt%.
Example 8: SEI-13162 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 2 wt%.
Example 9: SEI-13163 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 3 wt%.
Example 9 a: SEI-13164 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 4 wt%.
Example 10: SEI-13165 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the amount of the compound of formula 6 used as an additive was changed to 5 wt%.
Comparative example 1: SEI-13160 wt.%
An organic electrolyte solution was prepared in the same manner as in example 1, except that the compound of formula 6 was not used as an additive.
Production of lithium batteries (examples 1-1 to 3-1 and comparative example 1-1)
Examples 1 to 1
Manufacture of anodes
98 wt% of artificial graphite (BSG-L manufactured by Tianjin BTR new energy Technology co., Ltd.), 1.0 wt% of styrene-butadiene rubber (SBR) as a binder (manufactured by pulsatilla (Zeon)) and 1.0 wt% of carboxymethyl cellulose (CMC) (manufactured by japan a & L (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 anode active material slurry. The anode active material slurry was coated on a copper (Cu) current collector having a thickness of 10 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 ℃ for 0.5 hour, followed by further drying under the following conditions: the anode plate was manufactured in vacuum at 120 c for 4 hours, and then rolled.
Manufacture of cathodes
97.45 weight percent of LiNi1/3Co1/3Mn1/3O20.5 wt% of powder type artificial graphite (SFG 6 manufactured by termoku (Timcal)) as a conductive material, 0.7 wt% of carbon black (ketjen black manufactured by ECP), 0.25 wt% of modified acrylonitrile rubber (BM-720H manufactured by rieson Corporation), 0.9 wt% of polyvinylidene fluoride (PVDF manufactured by Solvay, S6020) and 0.2 wt% of PVDF (S5130 manufactured by Solvay) were mixed together, the mixture was added to N-methyl-2-pyrrolidone as a solvent, and the resulting solution was stirred using a mechanical stirrer for 30 minutes to prepare a cathode active material slurry. The cathode active material slurry was coated on an aluminum (Al) current collector having a thickness of 20 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 c for 0.5 hour, followed by further drying in vacuum at 120 c for 4 hours, and then rolled, thereby completing the manufacture of a cathode plate.
A polyethylene separator having a cathode side coated with ceramic and a thickness of 14 μm, and the organic electrolyte solution prepared according to example 1 were used to complete the fabrication of a lithium battery.
Examples 2-1 and 3-1
A lithium battery was fabricated in the same manner as in example 1-1, except that the organic electrolyte solutions prepared according to examples 2 and 3, respectively, were used instead of the organic electrolyte solution of example 1.
Comparative example 1-1
A lithium battery was fabricated in the same manner as in example 1-1, except that the organic electrolyte solution prepared according to comparative example 1 was used instead of the organic electrolyte solution of example 1.
Evaluation example 1: evaluation of Charge and discharge characteristics at 4.25V and Room temperature (25 ℃ C.)
Lithium batteries manufactured according to examples 1-1 to 3-1 and comparative example 1-1 were each charged at 25 ℃ with a constant current of 0.1C rate until the voltage reached 4.25V (with respect to Li), and then, while maintaining a constant voltage of 4.25V, the charging process was shut off with a current of 0.05C rate. Subsequently, each lithium battery was discharged at a constant current of 0.1C rate until the voltage reached 2.8V (with respect to Li) (formation operation, first cycle).
Each lithium cell was charged at 25 ℃ with a constant current of 0.2C rate after the first cycle of the forming operation until the voltage reached 4.25V (vs Li), and then the charging process was shut off with a current of 0.05C rate while maintaining a constant voltage of 4.25V. Subsequently, each lithium battery was discharged at a constant current of 0.2C rate until the voltage reached 2.8V (with respect to Li) (formation operation, second cycle).
Each lithium cell was charged at 25 ℃ with a constant current of 1.0C rate after the second cycle of the forming operation until the voltage reached 4.25V (relative to Li), and then the charging process was shut off with a current of 0.05C rate while maintaining a constant voltage of 4.25V. Subsequently, each lithium battery was discharged at a constant current of 1.0C rate until the voltage reached 2.75V (with respect to Li), and the charge and discharge cycle was repeated 380 times.
In all cycles of charge and discharge, there was a 10 minute rest period at the end of each cycle of charge/discharge.
A part of the charge and discharge experiment results are shown in table 1 below and fig. 1 and 2. The capacity retention at the 380 th cycle is defined using the following equation 1:
equation 1
Capacity retention rate [ discharge capacity at 380 th cycle/discharge capacity at first cycle ] × 100
TABLE 1
Figure BDA0002046587420000241
As shown in table 1 and fig. 1 and 2, the lithium batteries of examples 1-1 and 2-1 including the additive according to an 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 an additive.
Evaluation example 2: evaluation of Charge and discharge characteristics at 4.25V and high temperature (45 ℃ C.)
The lithium batteries of examples 1-1 to 3-1 and comparative example 1-1 were evaluated for charge and discharge characteristics using the same method as that used in evaluation example 1, except that the charge and discharge temperature was changed to 45 ℃. Meanwhile, the number of charge and discharge cycles was changed to 200 cycles.
A portion of the charge and discharge experimental results are shown in table 2 below and in fig. 3 and 4. The capacity retention at the 200 th cycle is defined using the following equation 2:
equation 2
Capacity retention rate [ discharge capacity at 200 th cycle/discharge capacity at first cycle ] × 100
TABLE 2
Figure BDA0002046587420000251
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 temperatures, as compared to the lithium battery of comparative example 1-1 not including such an additive.
Evaluation example 3: evaluation of Charge and discharge characteristics at 4.30V and Room temperature (25 ℃ C.)
The lithium batteries of example 1-1 and comparative example 1-1 were each charged at 25 ℃ with a constant current of 0.1C rate until the voltage reached 4.30V (with respect to Li), and then, while maintaining a constant voltage of 4.30V, the charging process was shut off with a current of 0.05C rate. Subsequently, each lithium battery was discharged at a constant current of 0.1C rate until the voltage reached 2.8V (with respect to Li) (formation operation, first cycle).
Each lithium cell was charged at 25 ℃ with a constant current of 0.2C rate after the first cycle of the forming operation until the voltage reached 4.30V (vs Li), and then the charging process was shut off with a current of 0.05C rate while maintaining a constant voltage of 4.30V. Subsequently, each lithium battery was discharged at a constant current of 0.2C rate until the voltage reached 2.8V (with respect to Li) (formation operation, second cycle).
Each lithium battery was charged at 25 deg.c at a constant current of 0.5C rate after the second cycle of the forming operation until the voltage reached 4.30V (with respect to Li), and then, the charging process was cut off at a current of 0.05C rate while maintaining a constant voltage of 4.30V. Subsequently, each lithium battery was discharged at a constant current of 1.0C rate until the voltage reached 2.75V (with respect to Li), and the charge and discharge cycle was repeated 250 times.
In all cycles of charge and discharge, there was a 10 minute rest period at the end of each cycle of charge/discharge.
A part of the charge and discharge experiment results are shown in the following table 3 and fig. 5. The capacity retention at cycle 250 is defined using equation 3 below:
equation 3
Capacity retention rate [ discharge capacity at 250 th cycle/discharge capacity at first cycle ] × 100
TABLE 3
Figure BDA0002046587420000261
As shown in table 3 and fig. 5, the lithium batteries of examples 1-1 including the additive according to the embodiments of the present disclosure exhibited significantly enhanced discharge capacity and life characteristics at room temperature, as compared to the lithium batteries of comparative examples 1-1 not including such an additive.
Evaluation example 4: evaluation of Charge and discharge characteristics at 4.30V and high temperature (45 ℃ C.)
The lithium batteries of example 1-1 and comparative example 1-1 were evaluated for charge and discharge characteristics using the same method as used in evaluation example 3, except that the charge and discharge temperature was changed to 45 ℃. Also, the number of charge and discharge cycles was changed to 200 cycles.
A part of the charge and discharge experiment results are shown in the following table 4 and fig. 6. The capacity retention at the 200 th cycle is defined using the following equation 4:
equation 4
Capacity retention rate [ discharge capacity at 200 th cycle/discharge capacity at first cycle ] × 100
TABLE 4
Figure BDA0002046587420000262
As shown in table 4 and fig. 6, the lithium batteries of examples 1-1 including the additive according to the embodiments of the present disclosure exhibited significantly enhanced discharge capacity and life characteristics at high temperatures, as compared to the lithium batteries of comparative examples 1-1 not including such an additive.
Evaluation example 5: evaluation of high temperature (60 ℃ C.) stability
The lithium batteries of examples 1-1 to 3-1 and comparative example 1-1 were subjected to the first cycle of charge and discharge as follows. Each lithium battery was charged at 25℃ with a constant current of 0.5C rate until the voltage reached 4.3V, and then, while maintaining a constant voltage of 4.3V, each lithium battery was charged until the current reached 0.05C, and then, was discharged with a constant current of 0.5C rate until the voltage reached 2.8V.
Each lithium battery was subjected to a second cycle of charging and discharging as follows. Each lithium battery was charged with a constant current of 0.5C rate until the voltage reached 4.3V, and then, while maintaining a constant voltage of 4.3V, each lithium battery was charged until the current reached 0.05C, and then, was discharged with a constant current of 0.2C rate until the voltage reached 2.8V.
Each lithium cell was subjected to a third cycle of charging and discharging as follows. Each lithium battery was charged with a constant current of 0.5C rate until the voltage reached 4.3V, and then, while maintaining a constant voltage of 4.3V, each lithium battery was charged until the current reached 0.05C, and then, was discharged with a constant current of 0.2C rate until the voltage reached 2.80V. The discharge capacity at the 3 rd cycle was regarded as a standard capacity.
Each lithium cell was subjected to the 4 th cycle of charging and discharging as follows. Each lithium battery was charged at a 0.5C rate until the voltage reached 4.30V, and then, while maintaining a constant voltage of 4.30V, each lithium battery was charged until the current reached 0.05C, the charged batteries were stored in an oven at 60 ℃ for 10 days and 30 days, and then, the batteries were taken out of the oven, and then, discharged at a 0.1C rate until the voltage reached 2.80V.
A portion of the charge and discharge evaluation results are shown in table 5 below. The capacity retention after high temperature storage is defined using the following equation 5:
equation 5
Capacity retention rate after high-temperature storage [% ] x100 [ discharge capacity at 4 th cycle at high temperature/standard capacity ] (herein, standard capacity is discharge capacity at 3 rd cycle)
TABLE 5
Capacity retention after 10 days storage [% ]] Capacity retention after 30 days storage [% ]]
Example 3-1 91 87
Comparative example 1-1 90 86
As shown in table 5, the lithium battery of example 3-1 including the organic electrolyte solution according to the embodiment of the present disclosure exhibited significantly enhanced high temperature stability, compared to the lithium battery of comparative example 1-1 not including the organic electrolyte solution of the present disclosure.
Evaluation example 6: evaluation of direct Current internal resistance (DC-IR) after high temperature (60 ℃) storage
The DC-IR of each of the lithium batteries of examples 1-1 to 3-1 and comparative example 1-1 was measured at room temperature (25 ℃ C.) using the following method, before being placed in a 60 ℃ oven, after being stored in a 60 ℃ oven for 10 days, and after being stored in a 60 ℃ oven for 30 days.
Each lithium cell was subjected to the first cycle of charging and discharging as follows. Each lithium battery was charged with a current of 0.5C until the voltage reached 50% SOC (state of charge), the charging process was cut off at 0.02C, and then, each lithium battery was allowed to stand for 10 minutes. Subsequently, each lithium battery was subjected to the following process: discharged at a constant current of 0.5C for 30 seconds followed by standing for 30 seconds, and charged at a constant current of 0.5C for 30 seconds followed by standing for 10 minutes; discharged at a constant current of 1.0C for 30 minutes, followed by standing for 30 seconds, and charged at a constant current of 0.5C for 1 minute, followed by standing for 10 minutes; discharged at a constant current of 2.0C for 30 seconds followed by standing for 30 seconds, and charged at a constant current of 0.5C for 2 minutes followed by standing for 10 minutes; discharged at a constant current of 3.0C for 30 seconds, followed by standing for 30 seconds, and charged at a constant current of 0.5C for 2 minutes, followed by standing for 10 minutes.
At each C-rate, the average voltage drop value for 30 seconds was a dc voltage value.
A part of the dc internal resistance increase calculated from the measured initial dc internal resistance and the dc internal resistance after the high-temperature storage is shown in table 6 below. The dc internal resistance increase is represented by the following equation 6:
equation 6
Dc internal resistance increase [% ] x100 [ dc internal resistance after high-temperature storage/initial dc internal resistance ] x
TABLE 6
Figure BDA0002046587420000281
As shown in table 6, the lithium battery of example 3-1 including the organic electrolyte solution according to the embodiment of the present disclosure exhibited a decrease in increase in direct current internal resistance after high temperature storage, compared to the lithium battery of comparative example 1-1 not including the organic electrolyte solution.
Production of lithium batteries (reference examples B1 to B4, examples B1 to B7 and comparative examples B1 to B3)
Reference example B1: artificial graphite, natural graphite 1:0+ SEI-13161 wt%
Manufacture of anodes
98 wt% of artificial graphite (AG-1 manufactured by shanshanshanshanshann co., ltd.), 1.0 wt% of SBR (manufactured by roly (Zeon)) as a binder, and 1.0 wt% of CMC (manufactured by japan a & L (NIPPON a & L)) were mixed together, the mixture was added to distilled water, and the resulting solution was stirred for 60 minutes using a mechanical stirrer, to prepare anode active material slurry. The anode active material slurry was coated on a Cu current collector having a thickness of 10 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 ℃ for 0.5 hour, followed by further drying at 120 ℃ in vacuum for 4 hours, and then rolled, thereby completing the fabrication of an anode plate.
Manufacture of cathodes
97.45 wt% of Li1.02Ni0.60Co0.20Mn0.20O20.5 wt% of powder type artificial graphite (SFG 6 manufactured by termoku (Timcal)) as a conductive material, 0.7 wt% of carbon black (ketjen black manufactured by ECP), 0.25 wt% of modified acrylonitrile rubber (BM-720H manufactured by rieson Corporation), 0.9 wt% of PVDF (S6020 manufactured by Solvay) and 0.2 wt% of PVDF (S5130 manufactured by Solvay) were mixed together, the mixture was added to N-methyl-2-pyrrolidone as a solvent, and the resulting solution was stirred using a mechanical stirrer for 30 minutes to prepare a cathode active material slurry. The cathode active material slurry was coated on an Al current collector having a thickness of 20 μm to a thickness of about 60 μm using a doctor blade, and the current collector was dried in a hot air dryer at 100 ℃ for 0.5 hour, followed by further drying in vacuum at 120 ℃ for 4 hours, and then rolled, thereby obtaining a cathode active material slurryThe manufacture of the cathode plate is completed.
The manufacture of a lithium battery was completed using a polyethylene separator having a thickness of 14 μm and having a cathode side coated with ceramic, and the organic electrolyte solution prepared according to example 1.
Example B1: artificial graphite, natural graphite 1:1+ SEI-13161 wt%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 1:1 was used as an anode active material.
Example B2 Artificial graphite Natural graphite 2:1+ SEI-13161 wt.%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 2:1 was used as an anode active material.
Example B3 Artificial graphite Natural graphite 3:1+ SEI-13160.5 wt.%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 3:1 was used as an anode active material, and that the organic electrolyte solution prepared according to example 3 was used as an electrolyte.
Example B4 Artificial graphite Natural graphite 3:1+ SEI-13160.7 wt.%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 3:1 was used as an anode active material, and that the organic electrolyte solution prepared according to example 6 was used as an electrolyte.
Example B5 Artificial graphite Natural graphite 3:1+ SEI-13161 wt.%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 3:1 was used as an anode active material.
Example B6 Artificial graphite Natural graphite 3:1+ SEI-13163 wt.%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 3:1 was used as an anode active material, and that the organic electrolyte solution prepared according to example 9 was used as an electrolyte.
Example B7 Artificial graphite Natural graphite 3:1+ SEI-13165 wt.%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 3:1 was used as an anode active material, and that the organic electrolyte solution prepared according to example 10 was used as an electrolyte.
Reference example B2 Artificial graphite, Natural graphite 0:1+ SEI-13161 wt%
A lithium battery was manufactured in the same manner as reference example B1, except that only natural graphite (C-SNG manufactured by Tianjin BTR new energy Technology co., Ltd.) was used as an anode active material instead of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshann co., Ltd.).
Reference example B3 Artificial graphite, Natural graphite 3:1+ SEI-13160.2 wt%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 3:1 was used as an anode active material, and that the organic electrolyte solution prepared according to example 4 was used as an electrolyte.
Reference example B4 Artificial graphite Natural graphite 4:1+ SEI-13161 wt%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 4:1 was used as an anode active material.
Comparative example B1 Artificial graphite Natural graphite 1:1+ SEI-13160 wt.%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 1:1 was used as an anode active material, and that an organic electrolyte solution prepared according to comparative example 1 was used as an electrolyte.
Comparative example B2 Artificial graphite Natural graphite 2:1+ SEI-13160 wt.%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 2:1 was used as an anode active material, and that the organic electrolyte solution of comparative example 1 was used as an electrolyte solution.
Comparative example B3 Artificial graphite Natural graphite 3:1+ SEI-13160 wt.%
A lithium battery was manufactured in the same manner as in reference example B1, except that a mixture of artificial graphite (AG-1 manufactured by shanshanshanshanshanshanshanshanshanshanshann co., Ltd.) and natural graphite (C-SNG manufactured by Tianjin BTR New Energy Technology co., Ltd.) in a weight ratio of 3:1 was used as an anode active material, and that the organic electrolyte solution of comparative example 1 was used as an electrolyte solution.
Evaluation example B1 evaluation of Charge and discharge characteristics at 4.25V and high temperature (45 ℃ C.)
The high-temperature charge and discharge characteristics of the lithium batteries manufactured according to examples B1 to B7, reference examples B1 to B4, and comparative examples B1 to B3 were evaluated.
A portion of the charge and discharge experimental results are shown in table B1 below. The capacity retention at the 200 th cycle is defined using the following equation 7:
equation 7
Capacity retention rate [ discharge capacity at 200 th cycle/discharge capacity at first cycle ] × 100
In table B1, the particle density refers to the density measured after pressing artificial graphite, natural graphite or a mixture thereof under a pressure of 2 tons.
TABLE B1
Figure BDA0002046587420000311
Figure BDA0002046587420000321
As shown in table B1, the lithium batteries of examples B1 to B7, which include the additive of the present disclosure, exhibited significantly enhanced life characteristics at high temperatures, as compared to the lithium batteries of comparative examples B1 to B3, which do not include such an additive.
Further, the lithium batteries of examples B1 to B7 containing artificial graphite and natural graphite within the specific amount range provided life characteristics similar to the lithium battery of reference example B1 containing only artificial graphite.
Evaluation example B2: evaluation of direct Current internal resistance (DC-IR) after high temperature (60 ℃ C.) storage
The lithium batteries of examples B1 to B7, reference examples B1 to B3, and comparative examples B1 to B3 were stored at high temperature, and then the DC-IR of each battery was measured using the same method as that used in evaluation example 6.
A portion of the DC-IR increase calculated from the initial DC-IR measured and the DC-IR measured after high temperature storage is shown in Table B2 below. The DC-IR growth is represented by the following equation 6:
equation 6
Dc internal resistance increase [% ] x100 [ dc internal resistance after high-temperature storage/initial dc internal resistance ] ×
TABLE B2
Figure BDA0002046587420000322
Figure BDA0002046587420000331
As shown in table B2, the lithium batteries of examples B1 through B7, which included the additives of the present disclosure, exhibited lower DC-IR growth than the lithium batteries of comparative examples B1 through B3, which did not include such additives.
In addition, each of the lithium batteries of examples B1 to B7 containing natural graphite within a specific amount range provided a DC-IR increase similar to that of the lithium battery of reference example B1 containing only artificial graphite.
By way of summary and review, aqueous electrolyte solutions that are highly active with respect to lithium may not be suitable for use in lithium batteries when such batteries are operated at high operating voltages. Lithium batteries generally use an organic electrolyte solution. The organic electrolyte solution is prepared by dissolving a lithium salt in an organic solvent. An organic solvent having stability at a high voltage, high ionic conductivity, high dielectric constant, and low viscosity may be used.
When a lithium battery uses a general organic electrolyte solution including a polar non-aqueous solvent of carbonate type, an irreversible reaction in which charges are excessively used due to a side reaction 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 SEI layers and/or protective layers may exhibit reduced stability at high temperatures.
Therefore, an organic electrolyte solution capable of forming an SEI layer and/or a protective layer having improved high temperature stability is desired.
Embodiments provide a lithium battery, including: comprises natural graphite; and an organic electrolyte solution anode, the organic electrolyte solution including a novel bicyclic sulfate-based additive. The lithium battery according to the embodiment exhibits enhanced high temperature characteristics and life characteristics.
Exemplary embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purposes of limitation. In some instances, features, characteristics and/or elements described in connection with a particular embodiment may be used alone or in combination with features, characteristics and/or elements described in connection with other embodiments, unless specifically indicated otherwise, as will be apparent to one of ordinary skill in the art at the time of filing the present application. It will therefore be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope as set forth in the following claims.

Claims (20)

1. A lithium battery, comprising:
a cathode including a cathode active material;
an anode including an anode active material; and
an organic electrolyte solution between the cathode and the anode,
wherein the anode active material comprises artificial graphite and natural graphite, the artificial graphite being present in an amount of 50 wt% or more based on the total weight of the anode active material; and is
The organic electrolyte solution includes a first lithium salt, an organic solvent, and a bicyclic sulfate-based compound represented by the following formula 1:
< formula 1>
Figure FDA0002046587410000011
Wherein, in formula 1, A1、A2、A3And A4Each independently a covalent bond, substituted or unsubstituted C1-C5Alkylene, carbonyl or sulfinyl, in which A1And A2Not all being covalent bonds and A3And A4Not all covalent bonds.
2. A lithium battery as claimed in claim 1, wherein a1、A2、A3And A4At least one of which is unsubstituted or substituted C1-C5Alkylene, wherein said substituted C1-C5The substituent of the alkylene group is at least one selected from the group consisting of: halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen substituted or unsubstituted C3-C20Heterocyclyl, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl or a polar functional group having at least one heteroatom.
3. A lithium battery as claimed in claim 1, wherein a1、A2、A3And A4At least one of which is unsubstituted or substituted C1-C5Alkylene, wherein said substituted C1-C5The substituent of the alkylene group is halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrafluorophenyl, pyrrolyl or pyridyl.
4. A lithium battery as in claim 2, wherein the substituted C is1-C5The substituent of alkylene 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) OR16、-OR16、-OC(＝O)OR16、-R15OC(＝O)OR16、-C(＝O)R16、-R15C(＝O)R16、-OC(＝O)R16、-R15OC(＝O)R16、-C(＝O)-O-C(＝O)R16、-R15C(＝O)-O-C(＝O)R16、-SR16、-R15SR16、-SSR16、-R15SSR16、-S(＝O)R16、-R15S(＝O)R16、-R15C(＝S)R16、-R15C(＝S)SR16、-R15SO3R16、-SO3R16、-NNC(＝S)R16、-R15NNC(＝S)R16、-R15N＝C＝S、-NCO、-R15-NCO、-NO2、-R15NO2、-R15SO2R16、-SO2R16、
Figure FDA0002046587410000021
Figure FDA0002046587410000022
Wherein, in the above formula, R11And R15Each independently halogen substituted or unsubstituted C1-C20Alkylene, halogen substituted or unsubstituted C2-C20Alkenylene, halogen substituted or unsubstituted C2-C20Alkynylene, halogen substituted or unsubstituted C3-C12Cycloalkylene, halogen substituted or unsubstituted C6-C40Arylene, halogen substituted or unsubstituted C2-C40Heteroarylene, halogen substituted or unsubstituted C7-C15Alkylarylene or halogen substituted or unsubstituted C7-C15An aralkylene group; and is
R12、R13、R14And R16Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C12Cycloalkyl, halogen substituted or unsubstituted C6-C40Aryl, halogen substituted or unsubstituted C2-C40Heteroaryl, halogen substituted or unsubstituted C7-C15Alkylaryl, halogen substituted or unsubstituted C7-C15Trialkylsilyl or halogen substituted or unsubstituted C7-C15An aralkyl group.
5. The lithium battery of claim 1, wherein the bicyclic sulfate-based compound is represented by formula 2 or 3:
Figure FDA0002046587410000031
wherein, in formulae 2 and 3, B1、B2、B3、B4、D1And D2Each independently is-C (E)1)(E2) -, carbonyl or sulfinyl; and is
E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C2-C20Alkenyl, halogen substituted or unsubstituted C2-C20Alkynyl, halogen substituted or unsubstituted C3-C20Cycloalkenyl, halogen substituted or unsubstituted C3-C20Heterocyclyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
6. A lithium battery as in claim 5, wherein E1And E2Each independently hydrogen, halogen substituted or unsubstituted C1-C10Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
7. A lithium battery as in claim 5, wherein E1And E2Each independently is hydrogen, fluoro, chloro, bromo, iodo, 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 5:
Figure FDA0002046587410000032
wherein, in formulae 4 and 5, R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently hydrogen, halogen substituted or unsubstituted C1-C20Alkyl, halogen substituted or unsubstituted C6-C40Aryl or halogen substituted or unsubstituted C2-C40A heteroaryl group.
9. The lithium battery of claim 8, wherein R1、R2、R3、R4、R21、R22、R23、R24、R25、R26、R27And R28Each independently hydrogen, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, trifluoromethyl, tetrafluoroethyl, phenyl, naphthyl, tetrakisFluorophenyl, pyrrolyl or pyridyl.
10. The lithium battery of claim 1, wherein the bicyclic sulfate-based compound is represented by one of the following formulas 6 to 17:
Figure FDA0002046587410000041
11. the lithium battery of claim 1, wherein the amount of the bicyclic sulfate-based compound is 0.4 to 5 wt% based on the total weight of the organic electrolyte solution.
12. The lithium battery of claim 1, wherein the amount of the bicyclic sulfate-based compound is 0.4 to 3 wt% based on the total weight of the organic electrolyte solution.
13. The lithium battery of claim 1, wherein the first lithium salt in the organic electrolyte solution comprises at least one selected from the group consisting of: LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiCF3SO3、Li(CF3SO2)2N、LiC4F9SO3、LiAlO2、LiAlCl4、LiN(CxF2x+1SO2)(CyF2y+1SO2) Wherein x is more than or equal to 2 and less than or equal to 20 and y is more than or equal to 2 and less than or equal to 20, LiCl and LiI.
14. The lithium battery of claim 1, wherein the organic electrolyte solution further comprises a cyclic carbonate compound, wherein the cyclic carbonate compound is selected from vinylene carbonate; vinylene carbonate substituted with at least one substituent selected from halogen, cyano and nitro; vinyl ethylene carbonate; vinyl ethylene 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.
15. The lithium battery of claim 14, wherein the amount of the cyclic carbonate compound is 0.01 wt% to 5 wt% based on the total weight of the organic electrolyte solution.
16. The lithium battery of claim 1, wherein the organic electrolyte solution further comprises a second lithium salt that is different from the first lithium salt and is represented by one of the following formulas 18-25:
Figure FDA0002046587410000051
Figure FDA0002046587410000061
17. the lithium battery of claim 16, wherein the amount of the second lithium salt is 0.1 to 5 wt% based on the total weight of the organic electrolyte solution.
18. The lithium battery as claimed in claim 1, wherein the amount of the natural graphite ranges from 25 wt% to 50 wt% based on the total weight of the anode active material.
19. The lithium battery of claim 1, wherein the cathode comprises a nickel-containing layered lithium transition metal oxide.
20. The lithium battery of claim 19, wherein the content of nickel in the lithium transition metal oxide is 60 mol% or more with respect to the total number of moles of transition metals.
CN201910360134.7A 2018-09-19 2019-04-30 Lithium battery Pending CN110931855A (en)

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