CN113299971A - Lithium ion battery and application thereof - Google Patents
Lithium ion battery and application thereof Download PDFInfo
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- CN113299971A CN113299971A CN202110552283.0A CN202110552283A CN113299971A CN 113299971 A CN113299971 A CN 113299971A CN 202110552283 A CN202110552283 A CN 202110552283A CN 113299971 A CN113299971 A CN 113299971A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a lithium ion battery and application thereof. The lithium ion battery comprises a positive plate and electrolyte; the positive plate comprises a positive current collector and a positive active layer arranged on at least one functional surface of the positive current collector; the positive electrode active layer comprises a positive electrode active material, and the positive electrode active material comprises cobalt element and aluminum element; the electrolyte comprises a nitrile compound; the mass percentage content A of the aluminum element in the positive active layer, the mass percentage content B of the cobalt element in the positive active layer and the mass percentage content C of the nitrile compound in the electrolyte meet the requirements that A/B is more than or equal to 0.008 and less than or equal to 0.018 and C/(A + B) is more than or equal to 0.03 and less than or equal to 0.085. The lithium ion battery has excellent cycle performance, safety performance under extreme temperature conditions (150 ℃) and overcharge prevention performance.
Description
Technical Field
The invention relates to a lithium ion battery and application thereof, belonging to the technical field of lithium ion batteries.
Background
In recent years, with the continuous expansion of the application field of lithium ion batteries, lithium ion batteries are important energy carriers in the fields of intelligent electronic products, large-scale energy storage power stations and electric automobiles, and the safety of lithium ion batteries is a key focus of people.
In the existing lithium ion battery, a stable interface is difficult to form between the positive active layer and the electrolyte, so that transition metal ions in the positive active layer can be dissolved out and electrolyte components can be oxidized and decomposed under the condition of high temperature or high voltage of the lithium ion battery, the temperature of the lithium ion battery can be further intensified, the lithium ion battery can be expanded, and the lithium ion battery can be caused to self-explode or fire.
Disclosure of Invention
The invention provides a lithium ion battery, wherein a stable interface can be formed between a positive active layer and an electrolyte of the lithium ion battery, and the lithium ion battery has good cycle performance and safety performance.
The invention provides an electronic device, wherein a stable interface can be formed between a positive active layer of a driving source and/or an energy storage source of the electronic device and an electrolyte, and the electronic device has good cycle performance and safety performance.
The invention provides a lithium ion battery, which comprises a positive plate and electrolyte;
the positive plate comprises a positive current collector and a positive active layer arranged on at least one functional surface of the positive current collector;
the positive electrode active layer comprises a positive electrode active material, and the positive electrode active material comprises cobalt element and aluminum element;
the electrolyte comprises a nitrile compound;
the mass percentage content A of the aluminum element in the positive electrode active layer, the mass percentage content B of the cobalt element in the positive electrode active layer, and the mass percentage content C of the nitrile compound in the electrolyte satisfy the following formulas (1) and (2):
0.008 is less than or equal to A/B is less than or equal to 0.018 formula (1)
C/(A + B) is more than or equal to 0.03 and less than or equal to 0.085, and the formula (2) is adopted.
The lithium ion battery as described above, wherein the nitrile compound is at least one selected from the group consisting of a compound of formula I, a compound of formula II, and a compound of formula III;
NC-R21-CN formula I
Wherein R is21、R22、R23Independently selected from substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C4-C10Heteroaryl, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C2-C10Unsaturated hydrocarbon group, substituted or unsubstituted C4-C10Heterocycloalkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C containing hetero atoms4-C10Carbonyl and substituted or unsubstituted C2-C10At least one of ether groups;
the substituents being selected from halogen and C containing hetero atoms4-C10At least one of alkyl groups.
The lithium ion battery as described above, wherein the compound of formula I is selected from at least one of succinonitrile, glutaronitrile, adiponitrile, sebaconitrile, nonadinitrile, dicyanobenzene, terephthalonitrile, pyridine-3, 4-dinitrile, 2, 5-dicyanopyridine, 2,3, 3-tetrafluorosuccinonitrile, tetrafluoroterephthalonitrile, 4-tetrahydrothiopyran methylenemalononitrile, fumarodinitrile, ethylene glycol bis (propionitrile) ether and 1,4,5, 6-tetrahydro-5, 6-dioxo-2, 3-pyrazinedicarboxonitrile; and/or the presence of a gas in the gas,
the compound of the formula II is selected from at least one of 1,3, 6-hexanetricarbonitrile, 1,3, 5-cyclohexanetricarbonitrile, 1,3, 5-benzenetricyanide, 1,2, 3-propanetricyanide and glycerol trinitrile; and/or the presence of a gas in the gas,
the compound of formula III is selected from at least one of 1,1,3, 3-propanetetracyanonitrile, 1,2,2, 3-tetracyanopropane, 1,2,4, 5-tetracyanobenzene, 2,3,5, 6-pyrazine tetracyanonitrile, 3-methyl-3-propyl-cyclopropane-1, 1,2, 2-tetracyanonitrile, 7,8, 8-tetracyanoterephthalenediquinodimethane and tetracyanoethylene.
The lithium ion battery as described above, wherein the electrolyte further comprises a phosphorus compound;
the phosphorus compound is at least one selected from trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, triallyl phosphate, tripropargyl phosphate, triphenyl phosphate, 1-propyl phosphoric anhydride, ethoxy pentafluorocyclotriphosphazene and phenoxy pentafluorocyclotriphosphazene.
The lithium ion battery as described above, wherein the phosphorus compound is contained in an amount of 0.1 to 10% by mass based on the total mass of the electrolyte.
The lithium ion battery as described above, wherein the electrolyte further comprises a sulfonate compound;
the sulfonate compound is at least one selected from 1, 3-propane sultone, 1, 3-propene sultone, 1-methyl-1, 3-propane sultone, 2-methyl-1, 3-propane sultone and 2-trifluoromethyl-1, 3-propane sultone.
The lithium ion battery as described above, wherein the sulfonate compound is contained in an amount of 0.5 to 2% by mass based on the total mass of the electrolyte.
The lithium ion battery as described above, wherein the electrolyte further comprises an organic solvent;
the organic solvent comprises a cyclic carbonate;
the organic solvent further includes at least one of a linear carbonate and a linear carboxylate.
The lithium ion battery as described above, wherein the cyclic carbonate is at least one selected from ethylene carbonate and propylene carbonate; and/or the presence of a gas in the gas,
the linear carbonate is at least one of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; and/or the presence of a gas in the gas,
the linear carboxylic ester is at least one selected from ethyl propionate, propyl propionate and propyl acetate.
The invention also provides an electronic device, wherein the driving source and/or the energy storage source of the electronic device comprise the lithium ion battery.
According to the invention, the anode containing the aluminum element and the cobalt element is matched with the electrolyte containing the nitrile compound, and the mass percentage content A of the aluminum element in the anode active layer, the mass percentage content B of the cobalt element in the anode active layer and the mass percentage content C of the nitrile compound in the electrolyte are matched, so that the cycle performance, the safety performance under the extreme temperature condition (150 ℃) and the overcharge prevention performance of the lithium ion battery can be improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first aspect of the invention provides a lithium ion battery, which comprises a positive plate and electrolyte;
the positive plate comprises a positive current collector and a positive active layer arranged on at least one functional surface of the positive current collector;
the positive electrode active layer comprises a positive electrode active material, and the positive electrode active material comprises cobalt element and aluminum element;
the electrolyte comprises a nitrile compound;
the mass percentage content A of the aluminum element in the positive electrode active layer, the mass percentage content B of the cobalt element in the positive electrode active layer and the mass percentage content C of the nitrile compound in the electrolyte satisfy the following formulas (1) and (2):
0.008 is less than or equal to A/B is less than or equal to 0.018 formula (1)
C/(A + B) is more than or equal to 0.03 and less than or equal to 0.085, and the formula (2) is adopted.
It is understood that the lithium ion battery of the present invention includes a positive electrode sheet and an electrolyte. The negative plate, the isolating film and the outer package are also included. The lithium ion battery can be obtained by stacking the positive plate, the isolating membrane and the negative plate to obtain the battery cell or stacking the positive plate, the isolating membrane and the negative plate, then winding to obtain the battery cell, placing the battery cell in an outer package, and injecting electrolyte into the outer package. The specific structure of the negative electrode sheet, the separator and the outer package is not particularly limited in the present invention, and may be selected from conventional negative electrode sheets, separators and outer packages in the art. For example, the negative electrode sheet may be a negative electrode sheet based on at least one of a carbon-based material, a silicon-based material, a tin-based material, or their corresponding alloy materials.
In the present invention, the functional surfaces refer to two surfaces of the current collector having the largest area and being oppositely disposed.
The positive plate can be obtained by arranging the positive active layer on one functional surface of the positive current collector, and can also be obtained by arranging the positive active layers on the two functional surfaces of the positive current collector.
The positive electrode active layer of the present invention includes a positive electrode active material, a conductive agent, and a binder.
The specific components of the positive electrode active material are not particularly limited in the present invention, and as long as the positive electrode active material contains cobalt element and aluminum element, the present invention is within the protection scope of the present invention.
The electrolytic solution of the present invention includes a nitrile compound, and the nitrile compound in the present invention refers to a cyano group-containing compound.
In the invention, the mass percentage content A of the aluminum element in the positive electrode active layer refers to the ratio of the mass of the aluminum element in the positive electrode active layer to the total mass of the positive electrode active layer; the mass percentage content B of the cobalt element in the positive electrode active layer refers to the ratio of the mass of the cobalt element in the positive electrode active layer to the total mass of the positive electrode active layer. In some embodiments, the mass percentage content a of the aluminum element and the mass percentage content B of the cobalt element in the positive electrode active layer may be tested using an inductively coupled plasma emission spectrometer (ICP).
The mass percentage content C of the nitrile compound in the electrolyte refers to the proportion of the mass of the nitrile compound in the electrode liquid in the total mass of the electrolyte.
According to the scheme provided by the invention, the cycle performance, the safety performance under the extreme temperature condition and the overcharge prevention performance of the lithium ion battery can be improved by matching the anode containing the aluminum element and the cobalt element with the electrolyte containing the nitrile compound and enabling A, B and C to satisfy 0.008-0.018 of A/B and 0.03-0.085 of C/(A + B), and the charge cut-off voltage of the obtained lithium ion battery can be 4.45V or more, for example, 4.45V, 4.48V, 4.5V, 4.53V and 4.55V. The inventors have analyzed that the reason for the improved performance of lithium ion batteries may be:
the atomic radius of the aluminum atoms in the positive active layer is similar to that of the cobalt atoms, so that the aluminum atoms and the cobalt atoms can be uniformly mixed under the condition of not influencing the transmission of lithium ions, the stability of the positive active layer can be improved, and the cycle performance, the safety performance under the extreme temperature condition and the overcharge prevention performance of the lithium ion battery can be improved; the nitrile compound in the electrolyte forms an interface protective film on the surface of the positive active layer, so that the positive active layer is prevented from contacting with the electrolyte under high pressure, the dissolution of cobalt ions in the positive active layer in the charging and discharging process is reduced, the deformation of the positive active layer in the charging and discharging process is prevented, and the cycle performance of the lithium ion battery is improved.
Furthermore, when A, B and C satisfy 0.008-0.018 of A/B and 0.03-0.085 of C/(A + B), the effects of cobalt element and aluminum element in the positive active layer and nitrile compound in the electrolyte can be fully exerted, on one hand, the content of nitrile compound in the electrolyte can be matched with the content of cobalt ion in the positive active layer, and the cyano in the electrolyte can fully complex the cobalt ion in the positive active layer to form a protective layer under the condition of not increasing the polarization of the lithium ion battery and not deteriorating the cycle performance of the lithium ion battery, so that the cobalt ion in the positive active layer is prevented from dissolving out, and the cycle performance of the lithium ion battery is improved; on the other hand, the function of the aluminum element in the positive active layer is fully exerted, the stability of the positive active layer can be improved, and the cycle performance, the safety performance under the extreme temperature condition and the overcharge prevention performance of the lithium ion battery are improved.
In some embodiments of the invention, the nitrile compound is selected from at least one of a compound of formula I, a compound of formula II, and a compound of formula III;
NC-R21-CN formula I
Wherein R is21、R22、R23Independently selected from substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C4-C10Heteroaryl, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C2-C10Unsaturated hydrocarbon group, substituted or unsubstituted C4-C10Heterocycloalkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C containing hetero atoms4-C10Carbonyl and substituted or unsubstituted C2-C10At least one of ether groups;
the substituents being selected from halogen and C containing hetero atoms4-C10At least one of alkyl groups.
As can be appreciated, C1-C10Alkyl is C1-C10Straight chain alkyl (e.g., methyl, ethyl, propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, etc.), C3-C10Branched alkyl (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, isohexyl, etc.) or C3-C10Cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.); c4-C10Heteroaryl refers to heteroaryl having 4 to 10 carbon atoms; c6-C10Aryl is aryl having 6 to 10 carbon atomsA group; c2-C10The unsaturated alkyl refers to alkyl containing at least one of carbon-carbon double bond and carbon-carbon triple bond with 2-10 carbon atoms, and can be unsaturated straight chain alkyl, unsaturated branched chain alkyl or unsaturated cyclic alkyl; c4-C10Heterocycloalkyl is C5-C11A group in which at least one carbon atom in the cycloalkyl group is substituted with a heteroatom; c1-C10Alkoxy means a straight or branched chain alkoxy group having 1 to 10 carbon atoms, and may be, for example, methoxy (-OCH)3) Ethoxy (-OCH)2CH3) N-propoxy group (-OCH)2 CH2CH3) I-propoxy (-OCH (CH)3)2) Etc.; c containing hetero atoms4-C10Carbonyl is C4-C10A group formed by substituting a carbon atom or a hydrogen atom in a carbonyl group with a heteroatom; c2-C10The ether group refers to a straight chain ether group or a branched chain ether group with 2-10 carbon atoms; halogen can be-F, -Cl, -Br, -I; c containing hetero atoms4-C10Alkyl refers to C4-C10A group formed by substituting a carbon atom or a hydrogen atom in an alkyl group with a heteroatom;
the hetero atom may be a nitrogen atom or a sulfur atom.
As non-limiting examples, the compound of formula I above may be selected from at least one of succinonitrile, glutaronitrile, adiponitrile, sebaconitrile, nonanedionitrile, dicyanobenzene, terephthalonitrile, pyridine-3, 4-dinitrile, 2, 5-dicyanopyridine, 2,3, 3-tetrafluorosuccinonitrile, tetrafluoroterephthalonitrile, 4-tetrahydrothiopyran methylenemalononitrile, fumaronitrile, ethyleneglycol bis (propionitrile) ether, and 1,4,5, 6-tetrahydro-5, 6-dioxo-2, 3-pyrazinedicarboxonitrile; and/or the presence of a gas in the gas,
the compound of formula II may be selected from at least one of 1,3, 6-hexanetricarbonitrile, 1,3, 5-cyclohexanetricarbonitrile, 1,3, 5-benzenetricyanide, 1,2, 3-propanetricyanide, and glycerol trinitrile; and/or the presence of a gas in the gas,
the compound of formula III may be selected from at least one of 1,1,3, 3-propanetetracyanonitrile, 1,2,2, 3-tetracyanopropane, 1,2,4, 5-tetracyanobenzene, 2,3,5, 6-pyrazinetetranitrile, 3-methyl-3-propyl-cyclopropane-1, 1,2, 2-tetracyanonitrile, 7,8, 8-tetracyanoterephthalenediquinodimethane and tetracyanoethylene.
In some embodiments of the invention, the electrolyte further comprises a phosphorus compound;
the phosphorus compound is at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, triallyl phosphate, tripropargyl phosphate, triphenyl phosphate, 1-propylphosphoric anhydride, ethoxypentafluorocyclotriphosphazene and phenoxypentafluorocyclotriphosphazene.
The inventors have found that when the above-described phosphorus compound is contained in the electrolyte, the cycle performance of the lithium ion battery can be further improved. The inventors speculate that the phosphorus compound can form a stable SEI film on the surface of the positive electrode active layer, and the cycle performance of the lithium ion battery is improved.
In the present invention, in order to provide a lithium ion battery with better cycle performance, in some embodiments of the present invention, the phosphorus compound is present in an amount of 0.1 to 10% by mass, based on the total mass of the electrolyte.
Illustratively, the phosphorus compound may be present in an amount of 0.1%, 0.5%, 1.0%, 1.5%, 2%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0% by mass.
In some embodiments of the invention, the electrolyte further comprises a sulfonate compound;
the sulfonate compound is at least one selected from 1, 3-propane sultone, 1, 3-propene sultone, 1-methyl-1, 3-propane sultone, 2-methyl-1, 3-propane sultone and 2-trifluoromethyl-1, 3-propane sultone.
The inventors have found in their research that the addition of the above sulfonate compound to the electrolyte can further improve the cycle performance of the lithium ion battery. The inventors speculate that the sulfonic acid ester compound can reduce the interface resistance between the negative electrode active layer and the electrolyte, and further improve the cycle performance of the lithium ion battery.
In the present invention, in order to better exert the function of the sulfonate compound and improve the cycle performance of the lithium ion battery, in some embodiments of the present invention, the sulfonate compound is contained in an amount of 0.5 to 2% by mass based on the total mass of the electrolyte.
Illustratively, the sulfonate compound may be present in an amount of 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0% by mass.
In some embodiments of the invention, the electrolyte further comprises an organic solvent;
the organic solvent includes a cyclic carbonate;
the organic solvent further includes at least one of a linear carbonate and a linear carboxylate.
According to the invention, by selecting the organic solvent in the electrolyte, the cycle performance and the safety performance of the lithium ion battery can be further improved on the premise of not influencing the charge and discharge performance of the lithium ion battery. It can be understood that, because the cyclic carbonate has the advantages of high dielectric constant and large viscosity, and the linear carbonate and the linear carboxylate have the advantages of low viscosity, when the cyclic carbonate and the linear carbonate or the linear carboxylate are used in combination, the advantages of high dielectric constant of the cyclic carbonate and the advantages of low viscosity of the linear carbonate and the linear carboxylate can be fully exerted, and the prepared electrolyte can improve the charge and discharge performance of the lithium ion battery on the premise of not influencing the cycle performance of the lithium ion battery.
Illustratively, the cyclic carbonate is selected from at least one of ethylene carbonate and propylene carbonate; and/or the presence of a gas in the gas,
the linear carbonate is at least one selected from dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; and/or the presence of a gas in the gas,
the linear carboxylic acid ester is at least one selected from ethyl propionate, propyl propionate and propyl acetate.
The lithium salt in the electrolyte solution is not particularly limited in the present invention, and may be a lithium salt commonly used in the art, and for example, the lithium salt may be at least one selected from the group consisting of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium tetrafluoroborate, lithium bis (trifluoromethanesulfonyl) imide, lithium difluorooxalato borate, and lithium bis (oxalato) borate.
A second aspect of the present invention provides an electronic device, wherein the drive source and/or the energy storage source of the electronic device comprise the lithium ion battery.
The lithium ion battery can be used as a power source of electronic equipment and also can be used as an energy storage unit of the electronic equipment. The electronic devices may include, but are not limited to, mobile devices (e.g., mobile phones, notebook computers, etc.), electric vehicles (e.g., electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, and the like.
The electronic equipment comprises the lithium ion battery, so that the electronic equipment has higher safety performance and longer service life.
The technical means of the present invention will be further described below with reference to specific examples.
Examples and comparative examples
The lithium ion batteries of the examples and comparative examples were prepared by the following steps:
1) preparation of positive plate
Mixing an anode active material lithium cobaltate doped with aluminum oxide or undoped aluminum oxide, a binder polyvinylidene fluoride (PVDF) and a conductive agent acetylene black according to a mass ratio of 97:1.5:1.5, adding N-methylpyrrolidone (NMP), and stirring under the action of a vacuum stirrer until a mixed system becomes anode active slurry with uniform fluidity; uniformly coating the positive active slurry on two functional surfaces of the aluminum foil; baking the coated aluminum foil in 5 sections of baking ovens with different temperature gradients, drying the aluminum foil in a baking oven at 120 ℃ for 8 hours, and rolling and slitting to obtain the required positive plate.
2) Preparation of negative plate
Mixing a negative active material graphite, a thickening agent sodium carboxymethyl cellulose (CMC-Na), a binder styrene butadiene rubber and a conductive agent acetylene black according to a mass ratio of 97:1:1:1, adding deionized water, and obtaining negative active slurry under the action of a vacuum stirrer; uniformly coating the negative active slurry on two functional surfaces of a copper foil with the thickness of 8 mu m; and (3) airing the coated copper foil at room temperature, then transferring the copper foil to an oven at 80 ℃ for drying for 10h, and then carrying out cold pressing and slitting to obtain the negative plate.
3) Preparation of the electrolyte
In a glove box filled with argon (H)2O＜0.1ppm，O2Less than 0.1ppm), uniformly mixing 15 mass percent of ethylene carbonate, 10 mass percent of propylene carbonate, 10 mass percent of diethyl carbonate and 65 mass percent of propyl propionate to obtain a mixed solution, and then quickly adding fully dried lithium hexafluorophosphate into the mixed solution, wherein the concentration of the lithium hexafluorophosphate is 1.25mol/L to form a basic electrolyte;
and respectively adding additives with different contents into the basic electrolyte, wherein the additives comprise nitrile compounds, phosphorus compounds and sulfonic acid ester compounds to obtain the electrolyte.
4) Preparation of lithium ion battery
Stacking the positive plate in the step 1), the negative plate in the step 2) and the isolation film in the order of the positive plate, the isolation film and the negative plate, and then winding to obtain a battery cell; placing the battery cell in an aluminum foil package, injecting the electrolyte in the step 3) into the package, and performing vacuum packaging, standing, formation, shaping, sorting and other processes to obtain a lithium ion battery;
among them, the separator was a polyethylene separator (available from Asahi chemical Co., Ltd.) having a thickness of 8 μm.
Specific preparation parameters are shown in table 1.
The following tests were performed on the lithium ion batteries obtained in the examples and comparative examples, respectively, and the test results are shown in table 2.
1) Cycle performance test
And (3) placing the corresponding obtained battery in a constant temperature environment at 25 ℃ to perform charge-discharge test at a rate of 1.0C/1.0C, wherein the cut-off voltage range is 3.0V-4.5V, the charge-discharge cycle is performed for 500 times, and the cycle discharge capacity is recorded and divided by the discharge capacity of the first cycle to obtain the cycle capacity retention rate.
2) Safety performance test under extreme temperature condition (150 ℃), and test method thereof
Charging at 25 deg.C under constant current of 0.5C to 4.48V, charging at constant voltage to cutoff current of 0.025C, standing for 2h, heating the battery in a hot box at a rate of 5 deg.C/min to 150 deg.C, maintaining for 60min, and determining the battery as PASS if it is not exploded or ignited, or else, FAIL.
3) Overcharge performance test
And (3) carrying out constant current charging to 5V at the rate of 3C at the temperature of 25 ℃, keeping the constant voltage of 5V for 8h, and observing whether the battery explodes or fires. If the battery is not exploded or ignited, the battery can be judged as PASS, otherwise, the battery is FAIL.
TABLE 1
TABLE 2
As can be seen from table 2, the cycle performance, the 150 ℃ safety performance test, and the overcharge performance of the lithium ion battery of the example of the present invention are superior to those of the lithium ion battery of the comparative example.
Further, as can be seen from examples 1 to 7, when A, B and C satisfy 0.008. ltoreq. A/B. ltoreq.0.018 and 0.03. ltoreq. C/(A + B). ltoreq.0.085 with the mass% of the nitrile compound in the electrolyte constant, the cycle performance of the lithium ion battery gradually increases as the sum of the mass% of the cobalt element and the mass% of the aluminum element in the positive electrode active layer increases.
From examples 1 to 4, it can be seen that the cycle performance of the lithium ion battery gradually increases as the mass percentage of aluminum element in the positive electrode active layer increases when A, B and C satisfy 0.008. ltoreq. a/B. ltoreq.0.018 and 0.03. ltoreq. C/(a + B). ltoreq.0.085, and the mass percentage of the nitrile compound in the electrolyte and the mass percentage of cobalt element in the positive electrode active layer are unchanged.
From examples 5 to 7, it can be seen that when A, B and C satisfy 0.008. ltoreq. a/B. ltoreq.0.018 and 0.03. ltoreq. C/(a + B). ltoreq.0.085, and the mass percentage content of the nitrile compound in the electrolyte and the mass percentage content of the aluminum element in the positive electrode active layer are unchanged, the mass percentage content of the cobalt element in the positive electrode active layer has no significant influence on the cycle performance of the lithium ion battery.
From examples 6 and 8 to 12, it can be seen that the cycle performance of the lithium ion battery gradually increases as the mass percentage of the nitrile compound in the electrolyte increases when A, B and C satisfy 0.008. ltoreq. a/B. ltoreq.0.018 and 0.03. ltoreq. C/(a + B). ltoreq.0.085 with the mass percentage of aluminum element and cobalt element in the positive electrode active layer unchanged.
From examples 9 to 12, it can be seen that A, B and C satisfy 0.008. ltoreq. A/B. ltoreq.0.018 and 0.03. ltoreq. C/(A + B). ltoreq.0.085, even if the mass percentages of the cobalt element and the aluminum element in the positive electrode active layer and the mass percentage of the nitrile compound in the electrolyte are not changed, the kind of the nitrile compound in the electrolyte is changed, and the cycle performance of the lithium ion battery is changed.
From examples 12, 13 and 15, it can be seen that when A, B and C satisfy 0.008. ltoreq. A/B. ltoreq.0.018 and 0.03. ltoreq. C/(A + B). ltoreq.0.085, and the mass percentages of the cobalt element and the aluminum element in the positive electrode active layer and the nitrile compound in the electrolyte are not changed, adding a phosphorus compound to the electrolyte increases the cycle performance of the lithium ion battery.
From examples 12, 14 and 16, it can be seen that when A, B and C satisfy 0.008. ltoreq. A/B. ltoreq.0.018 and 0.03. ltoreq. C/(A + B). ltoreq.0.085, and the mass percentages of the cobalt element and the aluminum element in the positive electrode active layer and the nitrile compound in the electrolyte are not changed, adding a sulfonate compound to the electrolyte increases the cycle performance of the lithium ion battery.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A lithium ion battery is characterized by comprising a positive plate and electrolyte;
the positive plate comprises a positive current collector and a positive active layer arranged on at least one functional surface of the positive current collector;
the positive electrode active layer comprises a positive electrode active material, and the positive electrode active material comprises cobalt element and aluminum element;
the electrolyte comprises a nitrile compound;
the mass percentage content A of the aluminum element in the positive electrode active layer, the mass percentage content B of the cobalt element in the positive electrode active layer, and the mass percentage content C of the nitrile compound in the electrolyte satisfy the following formulas (1) and (2):
A/B is more than or equal to 0.008 and less than or equal to 0.018 of formula (1);
C/(A + B) is more than or equal to 0.03 and less than or equal to 0.085, and the formula (2) is adopted.
2. The lithium ion battery of claim 1, wherein the nitrile compound is selected from at least one of a compound of formula I, a compound of formula II, and a compound of formula III;
NC-R21-CN formula I
Wherein R is21、R22、R23Independently selected from substituted or unsubstitutedC of (A)1-C10Alkyl, substituted or unsubstituted C4-C10Heteroaryl, substituted or unsubstituted C6-C10Aryl, substituted or unsubstituted C2-C10Unsaturated hydrocarbon group, substituted or unsubstituted C4-C10Heterocycloalkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C containing hetero atoms4-C10Carbonyl and substituted or unsubstituted C2-C10At least one of ether groups;
the substituents being selected from halogen and C containing hetero atoms4-C10At least one of alkyl groups.
3. The lithium ion battery of claim 2, wherein the compound of formula I is selected from at least one of succinonitrile, glutaronitrile, adiponitrile, sebaconitrile, nonadinitrile, dicyanobenzene, terephthalonitrile, pyridine-3, 4-dinitrile, 2, 5-dicyanopyridine, 2,3, 3-tetrafluorosuccinonitrile, tetrafluoroterephthalonitrile, 4-tetrahydrothiopyran methylenemalononitrile, fumaronitrile, ethylene glycol bis (propionitrile) ether, and 1,4,5, 6-tetrahydro-5, 6-dioxo-2, 3-pyrazinedicarboxyinitrile; and/or the presence of a gas in the gas,
the compound of the formula II is selected from at least one of 1,3, 6-hexanetricarbonitrile, 1,3, 5-cyclohexanetricarbonitrile, 1,3, 5-benzenetricyanide, 1,2, 3-propanetricyanide and glycerol trinitrile; and/or the presence of a gas in the gas,
the compound of formula III is selected from at least one of 1,1,3, 3-propanetetracyanonitrile, 1,2,2, 3-tetracyanopropane, 1,2,4, 5-tetracyanobenzene, 2,3,5, 6-pyrazine tetracyanonitrile, 3-methyl-3-propyl-cyclopropane-1, 1,2, 2-tetracyanonitrile, 7,8, 8-tetracyanoterephthalenediquinodimethane and tetracyanoethylene.
4. The lithium ion battery of any of claims 1-3, wherein the electrolyte further comprises a phosphorus compound;
the phosphorus compound is at least one selected from trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, triallyl phosphate, tripropargyl phosphate, triphenyl phosphate, 1-propyl phosphoric anhydride, ethoxy pentafluorocyclotriphosphazene and phenoxy pentafluorocyclotriphosphazene.
5. The lithium ion battery of claim 4, wherein the phosphorus compound is present in an amount of 0.1 to 10% by mass, based on the total mass of the electrolyte.
6. The lithium ion battery of any of claims 1-5, wherein the electrolyte further comprises a sulfonate compound;
the sulfonate compound is at least one selected from 1, 3-propane sultone, 1, 3-propene sultone, 1-methyl-1, 3-propane sultone, 2-methyl-1, 3-propane sultone and 2-trifluoromethyl-1, 3-propane sultone.
7. The lithium ion battery of claim 6, wherein the sulfonate compound is present in an amount of 0.5 to 2% by mass, based on the total mass of the electrolyte.
8. The lithium ion battery of any of claims 1-7, wherein the electrolyte further comprises an organic solvent;
the organic solvent comprises a cyclic carbonate;
the organic solvent further includes at least one of a linear carbonate and a linear carboxylate.
9. The lithium ion battery according to claim 8, wherein the cyclic carbonate is selected from at least one of ethylene carbonate and propylene carbonate; and/or the presence of a gas in the gas,
the linear carbonate is at least one of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; and/or the presence of a gas in the gas,
the linear carboxylic ester is at least one selected from ethyl propionate, propyl propionate and propyl acetate.
10. An electronic device, characterized in that a drive source and/or an energy storage source of the electronic device comprises a lithium ion battery according to any of claims 1-9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022149875A1 (en) * | 2021-01-07 | 2022-07-14 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte solution for lithium secondary battery, and lithium secondary battery comprising same |
| WO2024065431A1 (en) * | 2022-09-29 | 2024-04-04 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140356734A1 (en) * | 2013-05-31 | 2014-12-04 | Ningde Amperex Technology Limited | Electrolyte for lithium ion secondary battery and lithium ion secondary battery comprising the same |
| WO2015141179A1 (en) * | 2014-03-17 | 2015-09-24 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
| CN105140562A (en) * | 2015-07-23 | 2015-12-09 | 东莞市凯欣电池材料有限公司 | Electrolyte containing benzene dinitrile and lithium ion battery applying electrolyte |
| CN111326793A (en) * | 2018-12-14 | 2020-06-23 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN111900480A (en) * | 2020-08-21 | 2020-11-06 | 珠海冠宇电池股份有限公司 | High-voltage lithium ion battery with excellent high and low temperature performance |
-
2021
- 2021-05-20 CN CN202110552283.0A patent/CN113299971A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140356734A1 (en) * | 2013-05-31 | 2014-12-04 | Ningde Amperex Technology Limited | Electrolyte for lithium ion secondary battery and lithium ion secondary battery comprising the same |
| WO2015141179A1 (en) * | 2014-03-17 | 2015-09-24 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
| CN105140562A (en) * | 2015-07-23 | 2015-12-09 | 东莞市凯欣电池材料有限公司 | Electrolyte containing benzene dinitrile and lithium ion battery applying electrolyte |
| CN111326793A (en) * | 2018-12-14 | 2020-06-23 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN111900480A (en) * | 2020-08-21 | 2020-11-06 | 珠海冠宇电池股份有限公司 | High-voltage lithium ion battery with excellent high and low temperature performance |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022149875A1 (en) * | 2021-01-07 | 2022-07-14 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte solution for lithium secondary battery, and lithium secondary battery comprising same |
| WO2024065431A1 (en) * | 2022-09-29 | 2024-04-04 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
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