WO2022089127A1 - Batterie au lithium-ion - Google Patents

Batterie au lithium-ion Download PDF

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Publication number
WO2022089127A1
WO2022089127A1 PCT/CN2021/121196 CN2021121196W WO2022089127A1 WO 2022089127 A1 WO2022089127 A1 WO 2022089127A1 CN 2021121196 W CN2021121196 W CN 2021121196W WO 2022089127 A1 WO2022089127 A1 WO 2022089127A1
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carbonate
lithium ion
ion battery
group
carbon
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PCT/CN2021/121196
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English (en)
Chinese (zh)
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钱韫娴
胡时光
王勇
刘中波
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深圳新宙邦科技股份有限公司
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Publication of WO2022089127A1 publication Critical patent/WO2022089127A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • 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
    • 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
    • H01M10/44—Methods for charging or discharging
    • 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
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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

Definitions

  • the invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery.
  • lithium-ion batteries Due to the advantages of high operating voltage, wide operating temperature range, high energy density and power density, no memory effect and long cycle life, lithium-ion batteries have been widely used in the field of 3C digital products such as mobile phones and notebook computers, as well as in the field of new energy vehicles. Applications. In recent years, with the continuous development of thin and light 3C digital products, the battery industry's requirements for high energy density of lithium-ion batteries are getting higher and higher. Therefore, it is urgent to improve the energy density of lithium-ion batteries.
  • the separator While improving the energy density of lithium-ion batteries, it often brings serious safety problems. Among them, the separator has an important influence on the safety of the battery. If the battery shrinks and perforates the separator due to thermal runaway, the battery will short-circuit, posing a risk of fire and explosion. At present, most commercial lithium-ion battery separators are polyolefin separators, which thermally shrink at a temperature of 85°C or higher, posing a great safety hazard.
  • the inorganic particles such as SiO 2 , Al 2 O 3 , etc.
  • the use of organic or inorganic coated separators is the loss of battery performance in exchange for the improvement of safety performance. Therefore, how to reduce the negative impact on battery performance when using organic/inorganic coated separators is a problem that the lithium-ion battery industry needs to solve.
  • the purpose of the present invention is to overcome the problem of poor performance of lithium ion batteries using organic/inorganic coated separators in the prior art, and to provide a lithium ion battery that uses a separator with a coating to ensure that the battery At the same time of safety performance, it can also significantly improve the cycle performance and fast charging performance of the battery.
  • the inventors of the present invention have found through intensive research that when the separator of a lithium ion battery includes a substrate and a coating, the coating is coated on at least one side of the substrate, and the coating includes inorganic particles and/or PVDF, the non- When the compound represented by the formula (1) is added to the aqueous electrolyte, the cycle performance and fast charge performance of the lithium ion battery can be significantly improved, thereby completing the present invention.
  • the mechanism of action of the compound represented by formula (1) is not very clear, the inventors of the present invention speculate that the mechanism of action is that the inorganic particles of the separator usually contain active groups such as hydroxyl groups, which provide active sites for side reactions, As a result, side reactions occur with the electrolyte, resulting in capacity loss, and under high voltage conditions, these active sites will promote the dissolution of transition metal ions from the positive active material, which more significantly accelerates the side reactions of the electrolyte solution.
  • the compound represented by the formula (1) reacts with these active groups, and the resulting product adheres to the surface of the inorganic particles, reducing its side reaction with the electrolyte, thereby improving the cycle stability of the battery.
  • lithium-ion batteries using PVDF coatings generally adopt a hot-pressing formation process.
  • the compound represented by formula (1) will form a block polymer with PVDF, which is beneficial to The migration of lithium ions increases the conductivity of lithium ions, thereby improving the fast charging performance and cycling performance of lithium ion batteries.
  • the present invention provides a lithium ion battery
  • the lithium ion battery includes a positive electrode, a negative electrode, a separator placed between the positive electrode and the negative electrode, and a non-aqueous electrolyte,
  • the separator includes a substrate and a coating, the coating is applied to at least one side of the substrate, and the coating contains inorganic particles and/or PVDF.
  • the non-aqueous electrolyte solution contains an organic solvent, a lithium salt and a compound represented by the formula (1),
  • R 1 is a hydrocarbylene group having 2 to 20 carbon atoms, and the hydrocarbylene group contains one or more of a chain alkyl group, a cycloalkyl group and an aromatic group.
  • R 2 is one of an amine group, a group represented by the following formula (2), and a group represented by the following formula (3);
  • R 3 is one of an alkyl group having 1-10 carbon atoms, an ether group having 1-10 carbon atoms, an aryl group having 1-10 carbon atoms and an unsaturated hydrocarbon group having 2-10 carbon atoms, and R The hydrogen in 3 can be optionally substituted by halogen.
  • R 4 is one of an alkyl group having 1 to 6 carbon atoms and an ester group having 3 to 10 carbon atoms, and * represents a bonding position.
  • R 1 is a hydrocarbylene group having 3-15 carbon atoms, and the hydrocarbylene group contains one or more of a chain alkyl group, a cycloalkyl group and an aromatic group.
  • R 1 is one of the hydrocarbylene groups represented by the following structure, * represents the position of bonding,
  • R 4 is one of an alkyl group with 1-3 carbon atoms and an ester group with 3-5 carbon atoms;
  • R 2 is one of the groups represented by the following structures, * represents the position of binding,
  • the halogen is fluorine.
  • R 3 is one of the groups represented by the following structures, * represents the position of binding,
  • the compound represented by formula (1) is selected from one or more compounds having the following structures:
  • the content of the compound represented by formula (1) is 0.001% by weight or more; more preferably, in the non-aqueous electrolyte, the content of the compound represented by formula (1) is 0.001- 1 wt%.
  • the substrate is one or more of a porous polymer film, a single-layer or multi-layer porous polymer film laminate, and a porous non-woven fabric.
  • the porous polymer film is a polyolefin porous polymer film.
  • the non-woven fabric is one or more of glass fiber non-woven fabric, synthetic fiber non-woven fabric and ceramic fiber paper.
  • the thickness of the coating is 0.5-3 ⁇ m.
  • the inorganic particles are inorganic particles that do not undergo oxidation and/or reduction reactions within the battery operating voltage range; more preferably, the inorganic particles are one of Al 2 O 3 particles, SiO 2 particles and AlOOH particles one or more.
  • the particle size of the inorganic particles is 0.2-3 ⁇ m.
  • the active material of the positive electrode is LiNixCoyMzO 2 , wherein M is selected from Mn and/or Al, and 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.5, and x+y+z ⁇ 1.
  • the organic solvent is one or more of cyclic carbonate, linear carbonate, carboxylate and ether.
  • the cyclic carbonate includes one or more of ethylene carbonate, vinylene carbonate, propylene carbonate and butylene carbonate.
  • the linear carbonate includes one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propyl methyl carbonate.
  • the carboxylic acid esters include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate and ethyl trimethyl acetate one or more of the esters.
  • the ethers include ethylene glycol dimethyl ether, 1,3-dioxolane and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether one or more of.
  • the organic solvent is a mixture of ethylene carbonate and diethyl carbonate.
  • the lithium salt is selected from LiPF 6 , LiBF 4 , LiPO 2 F 2 , LiTFSI, LiBOB, LiDFOB, LiTFSI, LiSbF 6 , LiAsF 6 , LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 and one or more of LiN(SO 2 F) 2 ; more preferably, the lithium salt is LiPF 6 .
  • the content of the lithium salt in the non-aqueous electrolyte of the lithium ion battery is 0.5-3.5 mol/L; more preferably, the content of the lithium salt in the non-aqueous electrolyte of the lithium ion battery is 0.7-3.5 mol/L 1.5mol/L.
  • the non-aqueous electrolyte further contains additives, the additives are cyclic carbonate compounds with fluorine atoms, cyclic carbonate compounds with carbon-carbon unsaturated bonds, cyclic sulfonates One or more of compounds and nitrile compounds.
  • the additives are cyclic carbonate compounds with fluorine atoms, cyclic carbonate compounds with carbon-carbon unsaturated bonds, cyclic sulfonates One or more of compounds and nitrile compounds.
  • the cyclic carbonate compound having a fluorine atom is fluoroethylene carbonate and/or difluoroethylene carbonate.
  • the cyclic carbonate compound with carbon-carbon unsaturated bond is one or more of vinylene carbonate, vinyl ethylene carbonate, vinyl ethylene carbonate and vinylene methyl carbonate kind.
  • the cyclic sulfonate compound is 1,3-propane sultone and/or propylene sulfite.
  • the nitrile compounds are succinonitrile, adiponitrile, ethylene glycol bis(propionitrile) ether, hexanetrinitrile, adiponitrile, pimeliconitrile, suberonitrile, azelonitrile and sebacic acid one or more of nitriles.
  • the additive is fluoroethylene carbonate and/or succinonitrile.
  • the content of the additive is 0.1-5 wt % of the total weight of the non-aqueous electrolyte of the lithium ion battery.
  • the active material of the negative electrode is one or more of a metal material, a carbon-based negative electrode material and a non-carbon-based negative electrode material.
  • the metallic material includes metallic lithium.
  • the carbon-based negative electrode material includes one or more of graphite-based carbon materials, hard carbon materials and soft carbon materials.
  • the non-carbon-based negative electrode material includes one or more of silicon-based, tin-based, antimony-based, aluminum-based and transition metal compounds.
  • the active material of the negative electrode is artificial graphite.
  • the lithium ion battery provided by the present invention adopts a separator including a substrate and a coating, which can ensure that the battery has excellent safety performance.
  • the compound represented by formula (1) By adding the compound represented by formula (1) to the non-aqueous electrolyte, the high temperature and normal temperature cycle performance of the battery can be ensured, the capacity retention rate and cycle stability of the lithium ion battery can be improved, and the fast charging performance of the battery can be improved.
  • the present invention provides a lithium ion battery, wherein the lithium ion battery comprises a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte, the separator comprises a substrate and a coating layer, and the coating layer is coated Distributed on at least one side of the substrate, and the coating layer includes inorganic particles and/or PVDF; the non-aqueous electrolyte contains an organic solvent, a lithium salt and a compound represented by formula (1),
  • R 1 is a hydrocarbylene group having 2 to 20 carbon atoms, and the hydrocarbylene group contains one or more of a chain alkyl group, a cycloalkyl group and an aromatic group.
  • R 2 is one of an amine group, a group represented by the following formula (2), and a group represented by the following formula (3);
  • R 3 is one of an alkyl group having 1-10 carbon atoms, an ether group having 1-10 carbon atoms, an aryl group having 1-10 carbon atoms and an unsaturated hydrocarbon group having 2-10 carbon atoms, and R The hydrogen in 3 can be optionally substituted by halogen.
  • R 4 is one of an alkyl group having 1 to 6 carbon atoms and an ester group having 3 to 10 carbon atoms, and * represents a bonding position.
  • R 1 is a hydrocarbylene group with 3-15 carbon atoms, and the hydrocarbylene group contains one or more of a chain alkyl group, a cycloalkyl group and an aromatic group; more preferably, R 1 is one of the hydrocarbylene groups represented by the following structure, * represents the position of bonding,
  • R 2 is one of an amino group, a group represented by the following formula (2), and a group represented by the following formula (3).
  • R 4 is one of an alkyl group with 1-3 carbon atoms and an ester group with 3-5 carbon atoms.
  • R 2 is one of the groups represented by the following structure, * represents the position of binding,
  • R 3 is one of an alkyl group with 1-10 carbon atoms, an ether group with 1-10 carbon atoms, an aryl group with 1-10 carbon atoms and an unsaturated hydrocarbon group with 2-10 carbon atoms species, and the hydrogen in R3 may be optionally substituted by halogen.
  • a C1-C10 alkyl group a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a neobutyl group, a t-butyl group etc. are mentioned, for example.
  • Examples of the group in which hydrogen in the alkyl group having 1 to 10 carbon atoms is substituted by halogen include, for example, groups in which at least one hydrogen in each of the alkyl groups listed above is substituted with a halogen, and each of the alkyl groups listed above is preferred. A group in which one of the hydrogens is replaced by a halogen.
  • Examples of the unsaturated hydrocarbon group having 2 to 10 carbon atoms include a vinyl group, a propenyl group, an allyl group, a propynyl group, a propargyl group, a methyl vinyl group, and a methallyl group.
  • groups in which hydrogen in an unsaturated hydrocarbon group having 2 to 10 carbon atoms is substituted with halogen include, for example, groups in which at least one hydrogen in each of the unsaturated hydrocarbon groups listed above is substituted with halogen, and the above-mentioned groups are preferred.
  • the halogen is F, Cl, Br or I; more preferably, the halogen is F, Cl or Br; further preferably, the halogen is F or Cl; particularly preferably, the halogen is F .
  • R 3 is one of the groups represented by the following structure, * represents the position of binding,
  • the compound represented by formula (1) is selected from one or more compounds having the following structures:
  • the compound represented by the formula (1) can be obtained by those skilled in the art through organic synthesis.
  • it can be synthesized according to the following synthetic route:
  • a base can be used as an acid binding agent, and the compound represented by the formula (1) is obtained by amidation reaction of the primary amine as the compound A and the acid chloride as the compound B.
  • the conditions of the amidation reaction the conditions commonly used in the art can be adopted, for example, the molar ratio to the acid chloride of compound B can be 1:0.9-1.2;
  • the molar ratio of amine to base can be, for example, 1:1-3;
  • the reaction temperature can be room temperature, and the time can be more than 1 hour, preferably 1-24 hours.
  • the content of the compound represented by the formula (1) is 0.001% by weight; preferably, in the non-aqueous electrolyte of the lithium ion battery, the compound represented by the formula (1)
  • the content of the compound is 0.001-1% by weight; more preferably, the content of the compound represented by formula (1) in the non-aqueous electrolyte of the lithium ion battery is 0.2-0.5% by weight. If the content of the compound represented by formula (1) is lower than the above range, the improvement effect on the performance of the lithium ion battery is not obvious; if it exceeds the above range, the further improvement effect on the performance of the lithium ion battery is limited.
  • the separator comprises a substrate and a coating, the coating is applied to at least one side of the substrate, preferably, the coating is applied to both sides of the substrate.
  • the coating may contain inorganic particles and/or PVDF, for example, the coating may contain inorganic particles, may contain PVDF, or may contain both inorganic particles and PVDF.
  • the substrate can be various conventional membrane substrate materials in the field, for example, can be porous polymer film and porous non-woven fabric.
  • the porous polymer film may be used in a single layer, or may be a laminate of single or multi-layer porous polymer films.
  • the porous polymer film is a polyolefin porous polymer film.
  • the polyolefin for example, it can be polyethylene, polypropylene, etc., and can be various polyolefin materials conventional in the field. special restrictions.
  • the non-woven fabric can be various non-woven fabrics used in the field for lithium ion battery separators, without particular limitations, such as glass fiber non-woven fabrics, synthetic fiber non-woven fabrics and ceramic non-woven fabrics.
  • One or more of fiber paper are used in the field for lithium ion battery separators, without particular limitations, such as glass fiber non-woven fabrics, synthetic fiber non-woven fabrics and ceramic non-woven fabrics.
  • fiber paper One or more of fiber paper.
  • the thickness of the coating on the substrate can be the conventional thickness of the membrane coating in the field, preferably, the thickness of the coating is 0.5-3 ⁇ m, more preferably, the thickness of the coating is 0.5-2.5 ⁇ m, further preferably, the thickness of the coating is 1.5-2.5 ⁇ m.
  • the thickness of the coating By limiting the thickness of the coating to the above range, the safety performance of the battery can be ensured.
  • the inorganic particles may be various inorganic particles used in the field for coating lithium ion battery separators, as long as the inorganic particles do not undergo oxidation and/or reduction reactions within the operating voltage range of the lithium ion battery.
  • the inorganic particles are one or more of Al 2 O 3 particles, SiO 2 particles and AlOOH particles; more preferably, the inorganic particles are Al 2 O 3 particles.
  • the particle size of the inorganic particles is not particularly limited, and can be the size commonly used for coating separators in the field.
  • the particle size of the inorganic particles is 0.1-5 ⁇ m; more preferably, The particle size of the inorganic particles is 0.2-3 ⁇ m; further preferably, the particle size of the inorganic particles is 0.2-0.5 ⁇ m.
  • the preparation of the separator is not particularly limited, and can be carried out according to various methods commonly used in the art to prepare a separator by coating.
  • the coating material can be dispersed in a solvent to obtain a coating slurry, and then the coating slurry can be coated on the material used as the diaphragm substrate by a conventional coating method in the art, and then processed by drying and other processes, and then the coating slurry can be A coated separator was obtained.
  • materials such as conventional binders may also be added to the coating slurry, which will not be repeated here.
  • the active material of the positive electrode is not particularly limited.
  • the active material of the positive electrode is LiNixCoyMzO 2 , wherein M is selected from Mn and/or Al, and 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.5 , 0 ⁇ z ⁇ 0.5, x+y+z ⁇ 1.
  • the positive active material is LiCoO 2 ; for example, the x can be 0.8, y and z can be 0.1, M can be Mn, then the The positive electrode active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 . As long as the above relationship is satisfied, it will not be repeated here.
  • the organic solvent can be various organic solvents commonly used in the field to prepare non-aqueous electrolytes for lithium ion batteries, without particular limitations, for example, cyclic carbonates, linear carbonates, carboxylic acids can be used One or more of esters and ethers are used as organic solvents.
  • the cyclic carbonate used as the organic solvent for non-aqueous electrolysis of lithium ion batteries may include one or more of ethylene carbonate, vinylene carbonate, propylene carbonate and butylene carbonate.
  • the linear carbonate as the organic solvent for non-aqueous electrolysis of the lithium ion battery may include one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propyl methyl carbonate.
  • the carboxylate used as the organic solvent for non-aqueous electrolysis of lithium ion batteries may include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, and trimethyl acetic acid One or more of methyl ester and ethyl trimethylacetate.
  • the ethers as organic solvents for non-aqueous electrolysis of lithium ion batteries may include ethylene glycol dimethyl ether, 1,3-dioxolane, and 1,1,2,2-tetrafluoroethyl-2,2,3 , one or more of 3-tetrafluoropropyl ether.
  • the organic solvent is a mixture of ethylene carbonate and diethyl carbonate.
  • the lithium salt can be various lithium salts commonly used in the field to prepare lithium ion batteries, and there is no particular limitation.
  • LiPF 6 LiBF 4 , LiPO 2 F 2 , LiTFSI, LiBOB, LiDFOB, One or more of LiTFSI, LiSbF 6 , LiAsF 6 , LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 and LiN(SO 2 F) 2 .
  • the lithium salt is LiPF 6 .
  • the content of the lithium salt may be the usual content in the non-aqueous electrolyte of lithium ion batteries in the art, and is not particularly limited.
  • the content of the lithium salt in the non-aqueous electrolyte of the lithium ion battery may be 0.5-3.5 mol/L; preferably, the content of the lithium salt in the non-aqueous electrolyte of the lithium ion battery is 0.7-1.5 mol/L.
  • the content of the lithium salt is within this range, not only good battery performance can be achieved, but also the cost of the electrolyte can be effectively controlled.
  • the non-aqueous electrolyte for lithium ion batteries may further contain various additives commonly used in the art to improve the performance of lithium ion batteries, for example, the additives may be selected from cyclic carbonate compounds with fluorine atoms , one or more of cyclic carbonate compounds, cyclic sulfonate compounds and nitrile compounds having carbon-carbon unsaturated bonds.
  • the additives may be selected from cyclic carbonate compounds with fluorine atoms , one or more of cyclic carbonate compounds, cyclic sulfonate compounds and nitrile compounds having carbon-carbon unsaturated bonds.
  • the cyclic carbonate compound having a fluorine atom is fluoroethylene carbonate and/or difluoroethylene carbonate.
  • the cyclic carbonate compound with carbon-carbon unsaturated bond is one or more of vinylene carbonate, vinyl ethylene carbonate, vinyl ethylene carbonate and vinylene methyl carbonate kind.
  • the cyclic sulfonate compound is 1,3-propane sultone and/or propylene sulfite.
  • the nitrile compounds are succinonitrile, adiponitrile, ethylene glycol bis(propionitrile) ether, hexanetrinitrile, adiponitrile, pimeliconitrile, suberonitrile, azelonitrile and sebacic acid one or more of nitriles.
  • the additive is fluoroethylene carbonate and/or succinonitrile.
  • the content of the additive may be the conventional content of various additives in the lithium ion battery in the art.
  • the content of the additive may be 0.1-5% by weight of the total mass of the non-aqueous electrolyte of the lithium ion battery; preferably, the content of the additive may be 2% of the total mass of the non-aqueous electrolyte of the lithium ion battery -5 wt%.
  • the active material of the negative electrode material can be selected from various materials commonly used in the negative electrode active material of lithium ion batteries in the art, without special limitation, for example, the active material of the negative electrode can be a metal material, a carbon-based active material One or more of negative electrode materials and non-carbon-based negative electrode materials.
  • the metal material includes metal lithium
  • the carbon-based negative electrode material includes one or more of graphite-based carbon materials, hard carbon materials and soft carbon materials
  • the non-carbon-based negative electrode material includes silicon-based , one or more of tin-based, antimony-based, aluminum-based and transition metal compounds. More preferably, the active material of the negative electrode is artificial graphite.
  • the preparation of the positive electrode and the negative electrode of the lithium ion battery can be carried out according to the method commonly used in the art for preparing the positive electrode and the negative electrode of the lithium ion battery, and there is no particular limitation.
  • the active materials of the positive and negative electrodes may be mixed with a conductive agent, a binder, etc., and the resulting mixture may be dispersed in a solvent to prepare a slurry, and then the resulting slurry may be coated on a current collector and dried and rolled and so on.
  • the materials and substances commonly used in the art can be used for the conductive agent, solvent, current collector, etc., which will not be repeated here.
  • the preparation of the lithium ion battery can be carried out by the "sandwich" method commonly used in the art.
  • a separator is placed between the positive plate and the negative plate coated with the active material, and then the whole is wound, Then, the coiled body is flattened and placed in a packaging bag to be vacuum-baked and dried to obtain a battery cell. Then, the electrolyte is injected into the battery core, vacuum-sealed and left to stand for formation.
  • This method is a conventional method in the field and will not be repeated here.
  • the raw material compound A and raw material compound B in Table 1 were respectively subjected to amidation reaction at a molar ratio of 1:1 for 10 hours, and triethylamine was used as an acid binding agent (the ratio of triethylamine and raw material compound A) in the reaction.
  • the molar ratio is 1.5:1).
  • the compound 1, the compound 2, the compound 3, the compound 4, the compound 6, the compound 7 and the compound 12 are obtained by purification by column chromatography.
  • PVDF was added to acetone in an amount of 5% by weight relative to acetone, and dissolved at 50 ° C for 12 hours to prepare PVDF slurry; the PVDF slurry was coated on one side of Celgard2400 separator (thickness: 20 ⁇ m), and then After drying in an oven at 60 °C for 12 h, the thickness of the dried coating was 2 ⁇ m.
  • PVDF was added to acetone in an amount of 5% by weight relative to acetone, and dissolved at 50 ° C for 12 hours to prepare a PVDF mixed solution; Al 2 O 3 particles (particle size of 0.2 ⁇ m) were added to the PVDF mixed solution, Among them, the weight ratio of Al 2 O 3 particles to PVDF was 9:1, and Al 2 O 3 slurry was prepared; the Al 2 O 3 slurry was coated on one side of the Celgard2400 separator (thickness: 20 ⁇ m), and then the After drying in an oven at 60 °C for 12 h, the thickness of the coating after drying was 2 ⁇ m.
  • the PVDF slurry and Al 2 O 3 slurry prepared by the methods in Preparation Example 8 and Preparation Example 9 were coated on both sides of a Celgard2400 separator (thickness of 20 ⁇ m), and then dried in an oven at 60 ° C for 12 h, and then dried.
  • the coating thickness on the latter two sides is 2 ⁇ m.
  • Test Example 1 High temperature cycle performance test
  • the lithium-ion batteries prepared in the following examples and comparative examples were placed in an oven with a constant temperature of 45°C, charged to 4.2V (or 4.45V) at a constant current of 0.7C, and then charged at a constant voltage until the current dropped to 0.03C, and then Discharge to 3.0V at a constant current of 1C, cycle 400 times, record the first and last discharge capacities, and calculate the capacity retention rate of high-temperature cycles as follows:
  • Capacity retention rate (%) discharge capacity of the last cycle/discharge capacity of the first cycle ⁇ 100%.
  • Test example 2 normal temperature 3C fast charge cycle test
  • the lithium-ion batteries prepared in the following examples and comparative examples were placed in an incubator at 25°C, charged to 4.2V (or 4.45V) at a constant current of 3C, and then charged at a constant voltage until the current dropped to 0.03C, and then charged at a constant current of 3C to 0.03C.
  • the current constant current discharge to 3.0V, so cycle 200 times, record the first constant current charge capacity and total charge capacity, record the first discharge capacity and the last discharge capacity, calculate the 3C constant current charge as follows Proportion and capacity retention rate:
  • Constant current charging ratio (%) constant current charging capacity/total charging capacity ⁇ 100%;
  • Capacity retention ratio (%) last discharge capacity/first discharge capacity ⁇ 100%.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the positive active material LiCoO 2 , the conductive agent conductive carbon black Super-P, and the binder polyvinylidene fluoride (PVDF) were uniformly mixed in a weight ratio of 93:4:3, and then dispersed in N-methyl-2- In pyrrolidone (NMP), the positive electrode slurry is obtained; the positive electrode slurry is uniformly coated on both sides of the aluminum foil, dried, calendered and vacuum-dried, and the aluminum lead wire is welded with an ultrasonic welder to obtain the positive electrode.
  • the thickness is 110 ⁇ 2 ⁇ m.
  • the negative active material artificial graphite, the conductive agent conductive carbon black Super-P, and the binders styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) are mixed uniformly in a weight ratio of 94:1:2.5:2.5, and then the The mixture is dispersed in deionized water to obtain a negative electrode slurry; the negative electrode slurry is coated on both sides of the copper foil, dried, calendered and vacuum dried, and the nickel lead wire is welded with an ultrasonic welder to obtain a negative electrode, a polar plate
  • the thickness is 126 ⁇ 2 ⁇ m.
  • the PVDF-coated separator prepared in the above Preparation Example 8 was placed between the positive electrode and the negative electrode, and then the sandwich structure composed of the positive electrode, the negative electrode and the separator was wound, and the wound body was flattened and placed in an aluminum foil packaging bag. Bake under vacuum for 48h to obtain the cell to be injected;
  • hot-pressing is carried out according to the following steps: temperature 75°C, pressure 0.8MPa, 0.1C constant current charging for 45min, 0.2C constant current charging for 30min, then 0.5C constant current charging for 75min, secondary vacuum sealing, and then further charging at 0.2C Current constant current and constant voltage charge to cut-off voltage 4.45V, cut-off current 0.03C, and constant current discharge to 3.0V at 0.2C current.
  • the type and amount of the compound represented by formula (1) added to the non-aqueous electrolyte are different, the type of separator, the type of positive active material, the cut-off voltage, and the type and amount of additives are different.
  • Example 1-2 and Example 12-15 From the results of Example 1-2 and Example 12-15, it can be seen that among the compounds represented by formula (1) provided by the present invention, compounds 2, 3, 4, 6, 7, 12, etc. all have the same effect as compound 1 .

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Abstract

La présente invention concerne le domaine technique des batteries au lithium-ion, et l'invention concerne une batterie au lithium-ion, la batterie au lithium-ion comprenant une électrode positive, une électrode négative, un séparateur disposé entre l'électrode positive et l'électrode négative, et un électrolyte non aqueux ; le séparateur comprenant un substrat et un revêtement, le revêtement étant appliqué sur au moins une face du substrat, et le revêtement comprenant des particules inorganiques et/ou du PVDF ; et l'électrolyte non aqueux comprend un solvant organique, un sel de lithium et un composé de formule (1). La batterie au lithium-ion possède un séparateur doté d'un revêtement, ce qui améliore significativement les performances du cycle et la performance de charge rapide de la batterie tout en garantissant également la performance de sécurité de la batterie.
PCT/CN2021/121196 2020-10-30 2021-09-28 Batterie au lithium-ion WO2022089127A1 (fr)

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