WO2024124961A1 - 富锂锰基正极材料及其制备方法和应用 - Google Patents

富锂锰基正极材料及其制备方法和应用 Download PDF

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WO2024124961A1
WO2024124961A1 PCT/CN2023/115138 CN2023115138W WO2024124961A1 WO 2024124961 A1 WO2024124961 A1 WO 2024124961A1 CN 2023115138 W CN2023115138 W CN 2023115138W WO 2024124961 A1 WO2024124961 A1 WO 2024124961A1
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positive electrode
lithium
electrode material
rich manganese
preparation
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French (fr)
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伏萍萍
李红磊
吕菲
徐宁
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Tianjin B&M Science and Technology Co Ltd
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Tianjin B&M Science and Technology Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C01G53/502—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

  • layered oxides are widely used as cathode materials in commercial lithium-ion batteries due to their high platform voltage and relatively high specific capacity.
  • traditional cathode materials with moderate specific capacity cannot meet the range requirements of electric vehicles. Therefore, it is particularly necessary to develop a new generation of high energy density cathode materials.
  • Lithium-rich manganese-based layered cathode materials have a high specific capacity of more than 250mAh/g and a high operating voltage of 4.8V, and are low in cost, and have attracted widespread attention from researchers. Such a high specific capacity is because the Li2MnO3 component in the layered lithium-rich manganese-based cathode material participates in the reaction as an active phase at a charging voltage higher than 4.5V.
  • the layered lithium-rich manganese-based cathode materials still have the following key problems in practical use: 1) low initial efficiency in the first cycle due to oxygen release and irreversible movement of Li2O in the lattice; 2) poor rate performance due to low electronic conductivity and low ionic conductivity; 3) poor cycle stability; 4) voltage decay during the cycle.
  • the present disclosure provides a lithium-rich manganese-based positive electrode material, comprising a positive electrode material substrate and a coating layer coated on the surface of the positive electrode material substrate, wherein the coating layer comprises a carbon material doped with nitrogen and sulfur elements.
  • the positive electrode material matrix includes a material with a chemical formula of LiaNixCoyMn1 -xyO2 , wherein 1.04 ⁇ a ⁇ 1.24 , 0 ⁇ x ⁇ 0.2, and 0 ⁇ y ⁇ 0.1.
  • the carbon material doped with nitrogen and sulfur elements comprises a carbon material doped with nitrogen and sulfur elements formed by thermal decomposition of organic matter containing nitrogen and sulfur elements;
  • the organic matter containing nitrogen and sulfur elements includes one or more of L-cysteine and acetylcysteine.
  • the present disclosure provides a method for preparing the above-mentioned lithium-rich manganese-based positive electrode material, comprising the following steps:
  • the mixed material is subjected to a first calcination treatment in a protective atmosphere.
  • the mass ratio of the positive electrode material matrix to the organic matter containing nitrogen and sulfur elements is 100:(0.5-3).
  • an alcohol solvent is added when the positive electrode material matrix and the organic matter containing nitrogen and sulfur are mixed, and the alcohol solvent is removed to obtain the mixed material.
  • the alcohol solvent includes one or more of ethanol, n-propanol and isopropanol.
  • removing the alcohol solvent includes the following steps: stirring the positive electrode material matrix, the organic matter containing nitrogen and sulfur elements, and the alcohol solvent while heating them, the stirring speed is 300rpm/min to 600rpm/min, the heating temperature is 80°C to 100°C, and the insulation time is 15min to 30min.
  • the process conditions of the first calcination treatment include: calcination temperature of 250° C. to 400° C., and holding time of 2 h to 3 h;
  • the protective atmosphere comprises one or more of argon and nitrogen.
  • the method for preparing the positive electrode material matrix comprises the following steps: mixing the precursor and the lithium salt and then performing a second calcination treatment;
  • the precursor includes a material of the chemical formula Ni m Co n Mn 0.8-mn (OH) 2 , wherein 0 ⁇ m ⁇ 0.2, 0 ⁇ n ⁇ 0.1;
  • the lithium salt includes one or more of Li 2 CO 3 and LiOH;
  • the molar ratio of the metal element in the precursor to the lithium element in the lithium salt is 1:(1.3-1.6);
  • the calcination atmosphere of the second calcination treatment includes one or more of air and oxygen;
  • the process conditions of the second calcination treatment include: calcining the mixed precursor and the lithium salt at 450° C. to 600° C. for 4 h to 6 h, and then calcining at 850° C. to 1020° C. for 4 h to 6 h.
  • the present disclosure provides a positive electrode sheet, comprising the above-mentioned lithium-rich manganese-based positive electrode material or the lithium-rich manganese-based positive electrode material prepared by the above-mentioned preparation method.
  • the present disclosure provides a lithium-ion battery, comprising the above-mentioned positive electrode sheet.
  • the present disclosure provides an electrical device, comprising the lithium-ion battery.
  • the above-mentioned lithium-rich manganese-based positive electrode material and its preparation method and application have at least the following advantages:
  • the coating layer of the above-mentioned lithium-rich manganese-based positive electrode material contains a carbon material doped with nitrogen and sulfur elements.
  • the material has active sites and defects, which can improve the conductivity of electrons and ions, and can inhibit the agglomeration of the lithium-rich manganese-based positive electrode material during the cycle, thereby effectively improving the initial efficiency, cycle performance and multiple of the lithium-rich manganese-based positive electrode material. rate performance and reduce voltage attenuation.
  • FIG1 is a comparison chart of the first charge and discharge performance of the lithium-rich manganese-based positive electrode materials prepared in Examples 1 to 3 of the present disclosure and Comparative Example 1 under 1C conditions.
  • FIG2 is a comparison chart of the cycle performance of the lithium-rich manganese-based positive electrode materials prepared in Examples 1 to 3 of the present disclosure and Comparative Example 1 after 200 cycles at 0.5C.
  • FIG3 is a comparison chart of the rate performance of lithium-rich manganese-based positive electrode materials prepared in Examples 1 to 3 of the present disclosure and Comparative Example 1.
  • the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.
  • An embodiment of the present disclosure provides a lithium-rich manganese-based positive electrode material, including a positive electrode material substrate and a coating layer coated on the surface of the positive electrode material substrate, wherein the coating layer includes a carbon material doped with nitrogen and sulfur elements.
  • the coating layer of the lithium-rich manganese-based positive electrode material designed in the present invention contains carbon materials doped with nitrogen and sulfur elements.
  • the above-mentioned carbon materials have active sites and defects due to being doped with nitrogen and sulfur elements. Defects refer to carbon atoms in the carbon ring being replaced by N or S, thereby introducing excess electrons, which can improve the conductivity of electrons and ions, and at the same time inhibit the agglomeration of lithium-rich manganese-based positive electrode materials during the cycle process, thereby effectively improving the rate performance, first efficiency and cycle performance of lithium-rich manganese-based positive electrode materials, and reducing voltage attenuation.
  • the cathode material matrix includes a material having a chemical formula of LiaNixCoyMn1 -xyO2 , wherein 1.04 ⁇ a ⁇ 1.24, 0 ⁇ x ⁇ 0.2, and 0 ⁇ y ⁇ 0.1. It is understood that a can be any value between 1.04 and 1.24, for example, 1.04, 1.08, 1.12, 1.14, 1.18 , 1.22, or 1.24, etc., x can be, for example, 0, 0.05, 0.1, 0.15, or 0.2, etc., and y can be, for example, 0, 0.02, 0.04, 0.06, 0.08, or 0.1, etc.
  • the carbon material doped with nitrogen and sulfur includes a carbon material doped with nitrogen and sulfur formed by thermal decomposition of an organic substance containing nitrogen and sulfur.
  • the carbon material obtained by thermal decomposition of the organic substance containing nitrogen and sulfur is coated on the surface of the positive electrode material matrix. Since the obtained carbon material is doped with nitrogen and sulfur, the carbon material has active sites and defects, which can improve the conductivity of electrons and ions, and can inhibit the agglomeration of lithium-rich manganese-based positive electrode materials during the cycle, thereby effectively improving the rate performance, first efficiency and cycle performance of the lithium-rich manganese-based positive electrode material, and reducing voltage decay.
  • the organic matter containing nitrogen and sulfur elements includes one or more of L-cysteine and acetylcysteine.
  • L-cysteine is also known as La-amino-b-mercaptopropionic acid, and its molecular formula is C 3 H 7 NO 2 S, and the molecular formula of acetylcysteine is C 5 H 9 NO 3 S. Both of them can produce HS and NH3 by thermal decomposition, thereby forming a carbon material doped with nitrogen and sulfur elements.
  • L-cysteine and acetylcysteine are better in improving the rate performance, first efficiency and cycle performance of lithium-rich manganese-based positive electrode materials, and reducing voltage decay, and L-cysteine can be selected.
  • Another embodiment of the present disclosure provides a method for preparing the above-mentioned lithium-rich manganese-based positive electrode material, comprising the following steps:
  • the positive electrode material matrix and the organic matter containing nitrogen and sulfur are mixed to obtain a mixed material
  • the mixed material is subjected to a first calcination treatment in a protective atmosphere.
  • the above-mentioned mixed material is subjected to a first calcination treatment in a protective atmosphere, and a coating layer can be formed on the surface of the positive electrode material matrix.
  • the above-mentioned organic matter containing nitrogen and sulfur elements undergoes thermal decomposition during the calcination process to produce HS and NH3, forming a carbon material doped with nitrogen and sulfur elements, which can modify the surface of the positive electrode material matrix, improve the conductivity of electrons and ions, and at the same time inhibit the agglomeration of lithium-rich manganese-based positive electrode materials during the cycle process, thereby effectively improving the rate performance, first efficiency and cycle performance of lithium-rich manganese-based positive electrode materials, and reducing voltage attenuation.
  • the preparation method of the above-mentioned lithium-rich manganese-based positive electrode material is simple to operate, environmentally friendly, non-toxic and harmless, has strong economic adaptability, and is conducive to industrial application.
  • the mass ratio of the positive electrode material matrix and the organic matter containing nitrogen and sulfur elements is 100: (0.5-3). It should be noted that by controlling the mass ratio of the positive electrode material matrix and the organic matter containing nitrogen and sulfur elements, the mass ratio of the positive electrode material matrix and the carbon material doped with nitrogen and sulfur elements in the coating layer can be controlled. When the mass ratio of the positive electrode material matrix and the organic matter containing nitrogen and sulfur elements is too low, the improvement of the first efficiency and the reduction of voltage attenuation of the lithium-rich manganese-based positive electrode material are not obvious. When the mass ratio is too high, due to the large number of active sites and defects in the carbon material, it is not conducive to the improvement of the comprehensive performance of the lithium-rich manganese-based positive electrode material.
  • the mass ratio of the positive electrode material matrix and the organic matter containing nitrogen and sulfur elements can be, for example, 100:0.5, 100:1, 100:1.5, 100:2, 100:2.5 or 100:3.
  • an alcohol solvent is added when the positive electrode material matrix and the organic matter containing nitrogen and sulfur are mixed, and the alcohol solvent is removed to obtain a mixed material.
  • the alcohol solvent is added when the positive electrode material matrix and the organic matter containing nitrogen and sulfur are mixed in order to fully mix the positive electrode material matrix and the organic matter containing nitrogen and sulfur.
  • the alcohol solvent includes one or more of ethanol, n-propanol, and isopropanol.
  • removing the alcohol solvent comprises the following steps: stirring the positive electrode material matrix, the organic matter containing nitrogen and sulfur elements and the alcohol solvent while heating, the stirring speed is 300rpm/min to 600rpm/min, the heating temperature is 80°C to 100°C, and the insulation time is 15min to 30min.
  • the stirring speed can be, for example, 300rpm/min, 350rpm/min, 400rpm/min, 450rpm/min, 500rpm/min, 550rpm/min or 600rpm/min
  • the heating temperature can be any value between 80°C and 100°C, for example: 80°C, 82°C, 84°C, 86°C, 88°C, 90°C, 92°C, 94°C, 96°C, 98°C or 100°C
  • the insulation time can be, for example, 15min, 17min, 20min, 22min, 25min, 28min or 30min. Heating can be optionally heated in an oil bath.
  • the process conditions of the first calcination treatment include: a calcination temperature of 250°C to 400°C and a holding time of 2h to 3h. It is understood that the calcination temperature may be, for example, 250°C, 280°C, 300°C, 320°C, 350°C, 380°C or 400°C, and the holding time may be, for example, 2h, 2.5h or 3h.
  • the process conditions of the first calcination treatment further include: a heating rate of 3°C/min to 5°C/min. It is understood that the heating rate can be any value between 3°C/min and 5°C/min, for example: 3°C/min, 3.2°C/min, 3.5°C/min, 3.8°C/min, 4°C/min, 4.2°C/min, 4.5°C/min, 4.8°C/min or 5°C/min, etc.
  • the protective atmosphere includes one or more of argon and nitrogen.
  • the method for preparing a positive electrode material matrix includes the following steps: mixing a precursor and a lithium salt and then performing a second calcination treatment.
  • the precursor includes a material of the formula Ni m Co n Mn 0.8-mn (OH) 2 , wherein 0 ⁇ m ⁇ 0.2, 0 ⁇ n ⁇ 0.1. It is understood that m may be, for example, 0, 0.05, 0.1, 0.15 or 0.2, and n may be, for example, 0, 0.02, 0.04, 0.06, 0.08 or 0.1.
  • the lithium salt includes one or more of Li 2 CO 3 and LiOH.
  • the molar ratio of the metal element in the precursor to the lithium element in the lithium salt is 1:(1.3-1.6). It is understood that the molar ratio of the metal element in the precursor to the lithium element in the lithium salt can be, for example, 1:1.3, 1:1.4, 1:1.5 or 1:1.6.
  • the calcination atmosphere of the second calcination treatment includes one or more of air and oxygen.
  • the process conditions of the second calcination treatment include: mixing the precursor and the lithium salt in Calcine at 450°C to 600°C for 4h to 6h, and then calcine at 850°C to 1020°C for 4h to 6h.
  • calcining at 450°C to 600°C for 4h to 6h can be, for example, calcining at 450°C to 600°C for 6h, calcining at 500°C for 5.5h, calcining at 550°C for 5h, or calcining at 600°C for 4h, etc.
  • calcining at 850°C to 1020°C for 4h to 6h can be, for example, calcining at 850°C to 1020°C for 6h, calcining at 900°C for 5.5h, calcining at 950°C for 5h, or calcining at 1020°C for 4h to 6h.
  • a positive electrode sheet including the above-mentioned lithium-rich manganese-based positive electrode material or the lithium-rich manganese-based positive electrode material obtained by the above-mentioned preparation method.
  • the above-mentioned positive electrode sheet can be prepared, for example, by the following method: after mixing the above-mentioned lithium-rich manganese-based positive electrode material or the lithium-rich manganese-based positive electrode material obtained by the above-mentioned preparation method with a conductive agent and a binder, a solvent is added and stirred evenly to prepare a positive electrode slurry, and then the positive electrode slurry is coated on an aluminum foil, and the positive electrode sheet is obtained after drying and removing the solvent.
  • the present disclosure has no special restrictions on the above-mentioned conductive agent, the above-mentioned binder and the above-mentioned solvent, and the conductive agent, binder and solvent commonly used in the art can be used.
  • a lithium-ion battery including the above-mentioned positive electrode sheet.
  • the above-mentioned lithium-ion battery can be prepared, for example, by the following method: assemble the above-mentioned positive electrode sheet, diaphragm and negative electrode sheet with a shell after lamination or winding, inject electrolyte into the shell and then package it.
  • the active material of the above-mentioned negative electrode sheet can be one or more of graphite, hard carbon, silicon material, lithium titanate and metallic lithium, for example.
  • the present disclosure has no special restrictions on the above-mentioned diaphragm and the above-mentioned electrolyte, and the diaphragm and electrolyte commonly used in the art can be used.
  • an electric device comprising the above-mentioned lithium-ion battery.
  • the above-mentioned lithium-ion battery can be used as a power source or energy storage unit in the above-mentioned electric device, and the above-mentioned electric device includes but is not limited to electric vehicles, smart home appliances, computers, tablets, mobile phones, digital cameras, etc.
  • the instruments and raw materials used in the following examples are more specific, and in other specific embodiments, they may not be limited thereto; the weights of the relevant components mentioned in the embodiments of the present disclosure may not only refer to the specific content of each component, but may also represent the proportional relationship of the weights between the components, therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the description of the embodiments of the present disclosure, it is within the scope disclosed in the embodiments of the present disclosure.
  • the weights described in the description of the embodiments of the present disclosure may be mass units known in the chemical and chemical fields such as ⁇ g, mg, g, and kg.
  • the mass of the precursor Ni 0.2 Co 0.1 Mn 0.5 (OH) 2 is 3 g.
  • the weighed precursor Ni 0.2 Co 0.1 Mn 0.5 (OH) 2 and the lithium salt Li 2 CO 3 are mixed evenly in a stirrer. Then, the mixture was placed in a tube furnace and heated to 550°C at a heating rate of 3°C/min in air atmosphere and calcined for 5 hours. Then, the mixture was heated to 900°C at a heating rate of 5°C/min and calcined for 12 hours. After the temperature dropped to room temperature, a cathode material matrix was obtained, which included Li 1.2 Mn 0.5 Ni 0.2 Co 0.1 O 2 .
  • the obtained positive electrode material matrix, L-cysteine and anhydrous ethanol are fully stirred and mixed, and the obtained mixture is heated in an oil bath, and the anhydrous ethanol is removed to obtain a mixed material, wherein the mass of the positive electrode material matrix is 1 g, the mass ratio of the positive electrode material matrix to L-cysteine is 100:0.5, the volume of anhydrous ethanol is 25 mL, the heating temperature is 80°C, the stirring time is 15 min, and the stirring rate is 600 rpm/min;
  • an L-cysteine-derived N,S-doped carbon surface-modified lithium-rich manganese-based positive electrode material is obtained, that is, the coating layer of the lithium-rich manganese-based positive electrode material includes a carbon material doped with nitrogen and sulfur elements formed by thermal decomposition of L-cysteine.
  • the weighed precursor Ni 0.2 Co 0.1 Mn 0.5 (OH) 2 and the lithium salt Li 2 CO 3 are mixed evenly in a stirrer, and then placed in a tube furnace and heated to 550° C. at a heating rate of 3° C./min in an air atmosphere for calcination for 5 h, and then heated to 900° C. at a heating rate of 5° C./min for calcination for 12 h. After the temperature drops to room temperature, a positive electrode material matrix is obtained, and the positive electrode material matrix includes Li 1.2 Mn 0.5 Ni 0.2 Co 0.1 O 2 .
  • the obtained positive electrode material matrix, L-cysteine and anhydrous ethanol are fully stirred and mixed, and the obtained mixture is heated in an oil bath, and the anhydrous ethanol is removed to obtain a mixed material, wherein the mass of the positive electrode material matrix is 1 g, the mass ratio of the positive electrode material matrix to L-cysteine is 100:1, the volume of anhydrous ethanol is 25 mL, the heating temperature is 80°C, the stirring time is 15 min, and the stirring rate is 600 rpm/min;
  • an L-cysteine-derived N,S-doped carbon surface-modified lithium-rich manganese-based positive electrode material is obtained, that is, the coating layer of the lithium-rich manganese-based positive electrode material includes a carbon material doped with nitrogen and sulfur elements formed by thermal decomposition of L-cysteine.
  • the weighed precursor Ni 0.2 Co 0.1 Mn 0.5 (OH) 2 and the lithium salt Li 2 CO 3 are mixed evenly in a stirrer, and then placed in a tube furnace and heated to 550°C at a heating rate of 3°C/min in an air atmosphere for calcination for 5h, and then heated to 900°C at a heating rate of 5°C/min for calcination for 12h. After the temperature drops to room temperature, a positive electrode material matrix is obtained.
  • the positive electrode material matrix The body includes Li 1.2 Mn 0.5 Ni 0.2 Co 0.1 O 2 .
  • the obtained positive electrode material matrix, L-cysteine and anhydrous ethanol are fully stirred and mixed, and the obtained mixture is heated in an oil bath, and the anhydrous ethanol is removed to obtain a mixed material, wherein the mass of the positive electrode material matrix is 1 g, the mass ratio of the positive electrode material matrix to L-cysteine is 100:3, the volume of anhydrous ethanol is 25 mL, the heating temperature is 80°C, the stirring time is 15 min, and the stirring rate is 600 rpm/min;
  • an L-cysteine-derived N,S-doped carbon surface-modified lithium-rich manganese-based positive electrode material is obtained, that is, the coating layer of the lithium-rich manganese-based positive electrode material includes a carbon material doped with nitrogen and sulfur elements formed by thermal decomposition of L-cysteine.
  • the weighed precursor Ni 0.2 Co 0.1 Mn 0.5 (OH) 2 and the lithium salt Li 2 CO 3 are mixed evenly in a stirrer, and then placed in a tube furnace and heated to 550° C. at a heating rate of 3° C./min in an air atmosphere for calcination for 5 h, and then heated to 900° C. at a heating rate of 5° C./min for calcination for 12 h. After the temperature drops to room temperature, a positive electrode material matrix is obtained, and the positive electrode material matrix includes Li 1.2 Mn 0.5 Ni 0.2 Co 0.1 O 2 .
  • the obtained positive electrode material matrix, L-cysteine and anhydrous ethanol are fully stirred and mixed, and the obtained mixture is heated in an oil bath pot, and the anhydrous ethanol is removed to obtain a mixed material, wherein the mass of the positive electrode material matrix is 1g, the mass ratio of the positive electrode material matrix to L-cysteine is 100:0.2, the volume of anhydrous ethanol is 25mL, the heating temperature is 80°C, the stirring time is 15min, and the stirring rate is 600rpm/min;
  • an L-cysteine-derived N,S-doped carbon surface-modified lithium-rich manganese-based positive electrode material is obtained, that is, the coating layer of the lithium-rich manganese-based positive electrode material includes a carbon material doped with nitrogen and sulfur elements formed by thermal decomposition of L-cysteine.
  • the weighed precursor Ni 0.2 Co 0.1 Mn 0.5 (OH) 2 and the lithium salt Li 2 CO 3 are mixed evenly in a stirrer, and then placed in a tube furnace and heated to 550° C. at a heating rate of 3° C./min in an air atmosphere for calcination for 5 h, and then heated to 900° C. at a heating rate of 5° C./min for calcination for 12 h. After the temperature drops to room temperature, a positive electrode material matrix is obtained, and the positive electrode material matrix includes Li 1.2 Mn 0.5 Ni 0.2 Co 0.1 O 2 .
  • the obtained positive electrode material matrix, L-cysteine and anhydrous ethanol are fully stirred and mixed, and the obtained mixture is heated in an oil bath, and the anhydrous ethanol is removed to obtain a mixed material, wherein the mass of the positive electrode material matrix is 1 g, the mass ratio of the positive electrode material matrix to L-cysteine is 100:3.5, the volume of anhydrous ethanol is 25 mL, the heating temperature is 80°C, the stirring time is 15 min, and the stirring rate is 600 rpm/min;
  • an L-cysteine-derived N,S-doped carbon surface-modified lithium-rich manganese-based positive electrode material is obtained, that is, the coating layer of the lithium-rich manganese-based positive electrode material includes a carbon material doped with nitrogen and sulfur elements formed by thermal decomposition of L-cysteine.
  • the preparation method of lithium-rich manganese-based positive electrode material is as follows:
  • the weighed precursor Ni 0.2 Co 0.1 Mn 0.5 (OH) 2 and the lithium salt Li 2 CO 3 are mixed evenly in a stirrer, and then placed in a tube furnace and heated to 550° C. at a heating rate of 3° C./min in an air atmosphere for calcination for 5 hours, and then heated to 900° C. at a heating rate of 5° C./min for calcination for 12 hours. After the temperature drops to room temperature, a lithium-rich manganese-based positive electrode material is obtained, and the lithium-rich manganese-based positive electrode material includes Li 1.2 Mn 0.5 Ni 0.2 Co 0.1 O 2 .
  • the median voltage is the voltage value corresponding to half of the battery's discharge specific capacity.
  • the test results are shown in Table 1 and Figures 1 to 3.
  • the first discharge specific capacity, first efficiency and capacity retention rate of the lithium-rich manganese-based positive electrode materials prepared in Examples 1-5 are significantly higher, while the median voltage decay of the 200-cycle cycle is smaller, indicating that the carbon materials doped with nitrogen and sulfur elements in Examples 1-5 can effectively improve the first efficiency and cycle performance of the lithium-rich manganese-based positive electrode materials and reduce voltage decay.
  • the lithium-rich manganese-based positive electrode materials prepared in Examples 1-3 have a more obvious effect in improving the first efficiency and cycle performance and reducing voltage decay.
  • the rate performance of the lithium-rich manganese-based positive electrode materials prepared in Examples 1 to 3 is better than that of Comparative Example 1.
  • the lithium-rich manganese-based positive electrode materials prepared in Examples 4 to 5 were also subjected to the above rate performance test, and their rate performance was better than that of Comparative Example 1, indicating that the carbon materials doped with nitrogen and sulfur in Examples 1 to 5 can effectively improve the rate performance of the lithium-rich manganese-based positive electrode materials.
  • the lithium-rich manganese-based positive electrode material provided by the present disclosure includes a positive electrode material substrate and a coating layer coated on the surface of the positive electrode material substrate, and the coating layer includes a carbon material doped with nitrogen and sulfur elements.
  • the above-mentioned carbon material doped with nitrogen and sulfur elements includes a carbon material doped with nitrogen and sulfur elements formed by thermal decomposition of organic matter containing nitrogen and sulfur elements.
  • the lithium-rich manganese-based positive electrode material provided by the present disclosure can effectively improve the initial efficiency, cycle performance and rate performance of the battery, reduce voltage decay, and has excellent industrial applicability.

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Abstract

一种富锂锰基正极材料及其制备方法和应用，属于锂离子电池技术领域。富锂锰基正极材料包括正极材料基体和包覆在正极材料基体表面的包覆层，包覆层包括掺杂有氮元素和硫元素的碳材料。上述掺杂有氮元素和硫元素的碳材料包括由含氮元素和硫元素的有机物热分解形成的掺杂有氮元素和硫元素的碳材料。上述富锂锰基正极材料能够有效提高电池的首次效率、循环性能和倍率性能，减小电压衰减。

Description

富锂锰基正极材料及其制备方法和应用
相关申请的交叉引用
本公开要求于2022年12月15日提交中国专利局的申请号为202211618223.5、名称为“富锂锰基正极材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及锂离子电池技术领域，特别是涉及一种富锂锰基正极材料及其制备方法和应用。
背景技术
目前，层状氧化物因其高的平台电压和相对高的比容量作为正极材料被广泛地应用到商用锂离子电池领域。然而，拥有适中比容量的传统正极材料无法满足电动汽车的续航里程要求。因此，开发新一代高能量密度正极材料显得尤为必要。
富锂锰基层状正极材料具有超过250mAh/g的高比容量和4.8V的高工作电压，并且成本低廉，受到研究者的广泛关注。拥有如此高的比容量是因为层状富锂锰基正极材料中的Li2MnO3组分在充电电压高于4.5V下作为活性相参与反应。然而，层状富锂锰基正极材料在实际使用中仍然存在以下关键问题：1)因氧释放和晶格中Li2O不可逆移动导致的首周循环低的首次效率；2)低电子导电性和低离子导电性造成差的倍率性能；3)较差的循环稳定性；4)循环过程中出现的电压衰减。
发明内容
基于此，有必要提供一种能够提高电池首次效率、循环性能和倍率性能、减小电压衰减的富锂锰基正极材料及其制备方法和应用。
本公开提供一种富锂锰基正极材料，包括正极材料基体和包覆在所述正极材料基体表面的包覆层，所述包覆层包括掺杂有氮元素和硫元素的碳材料。
可选地，所述正极材料基体包括化学式为LiaNixCoyMn1-x-yO2的材料，其中，1.04≤a≤1.24，0≤x≤0.2，0≤y≤0.1。
可选地，所述掺杂有氮元素和硫元素的碳材料包括由含氮元素和硫元素的有机物热分解形成的掺杂有氮元素和硫元素的碳材料；
可选地，所述含氮元素和硫元素的有机物包括L-半胱氨酸和乙酰半胱氨酸中的一种或多种。
本公开提供一种上述富锂锰基正极材料的制备方法，包括以下步骤：
提供正极材料基体；
将所述正极材料基体和所述含氮元素和硫元素的有机物混合，得到混合物料；
将所述混合物料在保护性气氛中进行第一煅烧处理。
可选地，所述正极材料基体和所述含氮元素和硫元素的有机物的质量比为100：(0.5～3)。
可选地，所述正极材料基体和所述含氮元素和硫元素的有机物混合时还加入有醇类溶剂，去除所述醇类溶剂，得到所述混合物料。
可选地，所述醇类溶剂包括乙醇、正丙醇和异丙醇中的一种或多种。
可选地，去除所述醇类溶剂包括以下步骤：对所述正极材料基体、所述含氮元素和硫元素的有机物和所述醇类溶剂进行搅拌的同时进行加热，搅拌速度为300rpm/min～600rpm/min，加热的温度为80℃～100℃，保温的时间为15min～30min。
可选地，所述第一煅烧处理的工艺条件包括：煅烧温度250℃～400℃，保温时间2h～3h；
可选地，所述保护性气氛包括氩气和氮气中的一种或多种。
可选地，所述正极材料基体的制备方法包括以下步骤：将前驱体和锂盐混合后进行第二煅烧处理；
可选地，所述前驱体包括化学式NimConMn0.8-m-n(OH)2的材料，其中，0≤m≤0.2，0≤n≤0.1；
可选地，所述锂盐包括Li2CO3和LiOH中的一种或多种；
可选地，所述前驱体中的金属元素与所述锂盐中的锂元素的摩尔比为1：(1.3～1.6)；
可选地，所述第二煅烧处理的煅烧气氛包括空气和氧气中的一种或多种；
可选地，所述第二煅烧处理的工艺条件包括：将混合后的所述前驱体和所述锂盐在450℃～600℃下煅烧4h～6h，然后在850℃～1020℃下煅烧4h～6h。
本公开提供一种正极片，包括上述富锂锰基正极材料或上述制备方法制得的富锂锰基正极材料。
本公开提供一种锂离子电池，包括上述正极片。
本公开提供一种用电装置，包括上述锂离子电池。
与传统技术相比，上述富锂锰基正极材料及其制备方法和应用至少具有如下优点：
上述富锂锰基正极材料的包覆层中含有掺杂有氮元素和硫元素的碳材料，该材料具有活性位点和缺陷，能够提高电子的导电性和离子的导电性，同时能够抑制循环过程中富锂锰基正极材料发生团聚，从而能够有效提高富锂锰基正极材料的首次效率、循环性能和倍 率性能，减小电压衰减。
附图说明
图1为本公开实施例1～3和对比例1制备的富锂锰基正极材料在1C条件下的首次充放电性能对比图。
图2为本公开实施例1～3和对比例1制备的富锂锰基正极材料在0.5C条件下循环200周的循环性能对比图。
图3为本公开实施例1～3和对比例1制备的富锂锰基正极材料的倍率性能对比图。
具体实施方式
为使本公开的上述目的、特征和优点能够更加明显易懂，下面对本公开的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本公开。但是本公开能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本公开内涵的情况下做类似改进，因此本公开不受下面公开的具体实施例的限制。
在本公开的说明中，除非另有定义，未明确说明的专业术语、专业用词均与本领域技术人员通常理解的含义相同，且为本领域技术人员的公知常识，未明确说明的方法均为本领域技术人员公知的常规方法。本公开中术语“多种”的含义是至少两种，例如两种，三种等，除非另有明确具体的限定。
本公开中，以开放式描述的技术特征中，包括所列举特征组成的封闭式技术方案，也包括包含所列举特征的开放式技术方案。
本公开一实施方式提供一种富锂锰基正极材料，包括正极材料基体和包覆在正极材料基体表面的包覆层，包覆层包括掺杂有氮元素和硫元素的碳材料。
为了解决传统的富锂锰基正极材料的首次效率低、电压衰减严重、倍率性能差和循环性能差的问题，可以采用表面包覆、元素掺杂、异质结构、表面预处理和微纳结构等技术手段。其中，表面包覆能够有效保护电极材料，减少材料与电解液的副反应，防止锰离子溶解。由于碳材料具备较强的电子电导，将其用作富锂锰基的包覆层能够有效提高材料颗粒间的电导性，从而提升含有该材料的电池的倍率性能。但是，单一的碳包覆手段对于富锂锰基正极材料电化学性能的提升不够明显。因此，本公开设计富锂锰基正极材料的包覆层中含有掺杂有氮元素和硫元素的碳材料。上述碳材料由于掺杂有氮元素和硫元素而具有活性位点和缺陷，缺陷是指碳环中的碳原子被N或S取代，从而可以引入多余的电子，能够提高电子的导电性和离子的导电性，同时能够抑制循环过程中富锂锰基正极材料发生团聚，从而有效提高富锂锰基正极材料的倍率性能、首次效率和循环性能，减小电压衰减。
在一些实施方式中，正极材料基体包括化学式为LiaNixCoyMn1-x-yO2的材料，其中，1.04≤a≤1.24，0≤x≤0.2，0≤y≤0.1。可理解，a可以是1.04～1.24之间的任意值，例如：1.04、1.08、1.12、1.14、1.18、1.22或1.24等，x例如可以是0、0.05、0.1、0.15或0.2等，y例如可以是0、0.02、0.04、0.06、0.08或0.1等。
在一些实施方式中，掺杂有氮元素和硫元素的碳材料包括由含氮元素和硫元素的有机物热分解形成的掺杂有氮元素和硫元素的碳材料。上述含氮元素和硫元素的有机物经过热分解得到的碳材料包覆在正极材料基体的表面，由于得到的碳材料中掺杂有氮元素和硫元素，该碳材料中具有活性位点和缺陷，能够提高电子的导电性和离子的导电性，同时能够抑制循环过程中富锂锰基正极材料发生团聚，从而有效提高富锂锰基正极材料的倍率性能、首次效率和循环性能，减小电压衰减。
在一些实施方式中，含氮元素和硫元素的有机物包括L-半胱氨酸和乙酰半胱氨酸中的一种或多种。需要说明的是，L-半胱氨酸又称为L-a-氨基-b-巯基丙酸，其分子式为C3H7NO2S，乙酰半胱氨酸的分子式为C5H9NO3S，两者热分解均能产生HS和NH3，从而形成掺杂有氮元素和硫元素的碳材料。与其他含氮元素和硫元素的有机物相比，L-半胱氨酸和乙酰半胱氨酸在提高富锂锰基正极材料的倍率性能、首次效率和循环性能，减小电压衰减方面的效果更优，可选为L-半胱氨酸。
本公开另一实施方式提供一种上述富锂锰基正极材料的制备方法，包括以下步骤：
提供正极材料基体；
将正极材料基体和含氮元素和硫元素的有机物混合，得到混合物料；
将混合物料在保护性气氛中进行第一煅烧处理。
上述混合物料在保护性气氛中进行第一煅烧处理，能够在正极材料基体的表面形成包覆层。上述含氮元素和硫元素的有机物在煅烧过程中发生热分解产生HS和NH3，形成掺杂有氮元素和硫元素的碳材料，能够对正极材料基体的表面进行修饰，提高电子的导电性和离子的导电性，同时能够抑制循环过程中富锂锰基正极材料发生团聚，从而有效提高富锂锰基正极材料的倍率性能、首次效率和循环性能，减小电压衰减。并且上述富锂锰基正极材料的制备方法操作简单，环保，无毒无害，经济适应性强，有利于工业化应用。
在一些实施方式中，正极材料基体和含氮元素和硫元素的有机物的质量比为100：(0.5～3)。需要说明的是，通过控制正极材料基体和含氮元素和硫元素的有机物的质量比，可以控制正极材料基体与包覆层中掺杂有氮元素和硫元素的碳材料的质量比。当正极材料基体和含氮元素和硫元素的有机物的质量比过低时，对于富锂锰基正极材料的首次效率的提升和电压衰减的减少不明显，当质量比过高时，由于碳材料中的活性位点和缺陷较多，反而不利于富锂锰基正极材料的综合性能的提升。
可理解，正极材料基体和含氮元素和硫元素的有机物的质量比例如可以是100：0.5、100：1、100：1.5、100：2、100：2.5或100：3等。
在一些实施方式中，正极材料基体和含氮元素和硫元素的有机物混合时还加入有醇类溶剂，去除醇类溶剂，得到混合物料。上述正极材料基体与含氮元素和硫元素的有机物混合时还加入有醇类溶剂，是为了将正极材料基体和含氮元素和硫元素的有机物充分混合均匀。
在一些实施方式中，醇类溶剂包括乙醇、正丙醇和异丙醇中的一种或多种。
在一些实施方式中，去除醇类溶剂包括以下步骤：对正极材料基体、含氮元素和硫元素的有机物和醇类溶剂进行搅拌的同时进行加热，搅拌速度为300rpm/min～600rpm/min，加热的温度为80℃～100℃，保温的时间为15min～30min。可理解，搅拌速度例如可以是300rpm/min、350rpm/min、400rpm/min、450rpm/min、500rpm/min、550rpm/min或600rpm/min等，加热的温度可以是80℃～100℃之间的任意值，例如：80℃、82℃、84℃、86℃、88℃、90℃、92℃、94℃、96℃、98℃或100℃等，保温的时间例如可以是15min、17min、20min、22min、25min、28min或30min等。加热可选油浴加热。
在一些实施方式中，第一煅烧处理的工艺条件包括：煅烧温度250℃～400℃，保温时间2h～3h。可理解，煅烧温度例如可以是250℃、280℃、300℃、320℃、350℃、380℃或400℃等，保温时间例如可以是2h、2.5h或3h等。
在一些实施方式中，第一煅烧处理的工艺条件还包括：升温速率为3℃/min～5℃/min。可理解，升温速率可以是3℃/min～5℃/min之间的任意值，例如：3℃/min、3.2℃/min、3.5℃/min、3.8℃/min、4℃/min、4.2℃/min、4.5℃/min、4.8℃/min或5℃/min等。
在一些实施方式中，保护性气氛包括氩气和氮气中的一种或多种。
在一些实施方式中，正极材料基体的制备方法包括以下步骤：将前驱体和锂盐混合后进行第二煅烧处理。
在一些实施方式中，前驱体包括化学式NimConMn0.8-m-n(OH)2的材料，其中，0≤m≤0.2，0≤n≤0.1。可理解，m例如可以是0、0.05、0.1、0.15或0.2等，n例如可以是0、0.02、0.04、0.06、0.08或0.1等。
在一些实施方式中，锂盐包括Li2CO3和LiOH中的一种或多种。
在一些实施方式中，前驱体中的金属元素与锂盐中的锂元素的摩尔比为1：(1.3～1.6)。可理解，前驱体中的金属元素与锂盐中的锂元素的摩尔比例如可以是1：1.3、1：1.4、1：1.5或1：1.6等。
在一些实施方式中，第二煅烧处理的煅烧气氛包括空气和氧气中的一种或多种。
在一些实施方式中，第二煅烧处理的工艺条件包括：将混合后的前驱体和锂盐在 450℃～600℃下煅烧4h～6h，然后在850℃～1020℃下煅烧4h～6h。可理解，450℃～600℃下煅烧4h～6h例如可以是450℃下煅烧6h，500℃下煅烧5.5h，550℃下煅烧5h或600℃下煅烧4h等，850℃～1020℃下煅烧4h～6h例如可以是850℃下煅烧6h，900℃下煅烧5.5h，950℃下煅烧5h或1020℃下煅烧4h等。
本公开另一实施方式提供一种正极片，包括上述富锂锰基正极材料或上述制备方法制得的富锂锰基正极材料。需要说明的是，上述正极片例如可以由以下方法制得：将上述富锂锰基正极材料或上述制备方法制得的富锂锰基正极材料与导电剂、粘结剂混合后，加入溶剂搅拌均匀制备成正极浆料，然后将正极浆料涂覆在铝箔上，经干燥处理去除溶剂后得到正极片。本公开对上述导电剂、上述粘结剂和上述溶剂没有特别的限制，采用本领域常用的导电剂、粘结剂和溶剂即可。
本公开另一实施方式提供一种锂离子电池，包括上述正极片。需要说明的是，上述锂离子电池例如可以由以下方法制备：将上述正极片、隔膜和负极片经叠片或者卷绕后与壳体组装，向壳体内注入电解液后封装得到。上述负极片的活性物质例如可以是石墨、硬炭、硅材料、钛酸锂和金属锂中的一种或多种，本公开对上述隔膜和上述电解液没有特别的限制，采用本领域常用的隔膜和电解液即可。
本公开另一实施方式提供一种用电装置，包括上述锂离子电池。需要说明的是，上述锂离子电池可以作为电源或者能量储存单元用于上述用电装置中，上述用电装置包括但不限于电动车辆、智能家电产品、电脑、平板、手机、数码相机等。
以下结合具体实施例和对比例对本公开做进一步详细的说明。以下具体实施例中未写明的实验参数，优先参考本公开文件中给出的指引，还可以参考本领域的实验手册或本领域已知的其它实验方法，或者参考厂商推荐的实验条件。可理解，以下实施例所用的仪器和原料较为具体，在其他具体实施例中，可不限于此；本公开说明书实施例中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本公开实施例说明书相关组分的含量按比例放大或缩小均在本公开说明书实施例公开的范围之内。具体地，本公开实施例说明书中所述的重量可以是μg、mg、g、kg等化学化工领域公知的质量单位。
以下实施例和对比例中，配锂量Li：M(Ni,Co,Mn)＝X，指的是锂盐中的锂元素与前驱体中的金属元素的摩尔比为X。
实施例1
1、制备正极材料基体
前驱体Ni0.2Co0.1Mn0.5(OH)2的质量为3g，按照配锂量Li：M(Ni,Co,Mn)＝1.5计算锂盐Li2CO3的质量。将称取的前驱体Ni0.2Co0.1Mn0.5(OH)2和锂盐Li2CO3在搅拌器中混合均匀， 然后置于管式炉中在空气气氛中以3℃/min的升温速率升温到550℃煅烧5h，再以5℃/min的升温速率升温到900℃煅烧12h，待温度降至室温后，得到正极材料基体，该正极材料基体包括Li1.2Mn0.5Ni0.2Co0.1O2。
2、制备富锂锰基正极材料
S1.将得到的正极材料基体、L-半胱氨酸和无水乙醇充分搅拌混合，将得到的混合物料利用油浴锅加热，去除无水乙醇后得到混合物料，其中，正极材料基体的质量为1g，正极材料基体与L-半胱氨酸的质量比为100：0.5，无水乙醇的体积为25mL，加热温度为80℃，搅拌时间为15min，搅拌速率为600rpm/min；
S2.将混合物料置于管式炉中，在氩气气氛中以350℃煅烧2h，待温度降至室温后，得到L-半胱氨酸衍生的N,S掺杂碳表面修饰富锂锰基正极材料，即富锂锰基正极材料的包覆层中包括由L-半胱氨酸热分解形成的掺杂有氮元素和硫元素的碳材料。
实施例2
1、制备正极材料基体
前驱体Ni0.2Co0.1Mn0.5(OH)2的质量为3g，按照配锂量Li：M(Ni,Co,Mn)＝1.5计算锂盐Li2CO3的质量。将称取的前驱体Ni0.2Co0.1Mn0.5(OH)2和锂盐Li2CO3在搅拌器中混合均匀，然后置于管式炉中在空气气氛中以3℃/min的升温速率升温到550℃煅烧5h，再以5℃/min的升温速率升温到900℃煅烧12h，待温度降至室温后，得到正极材料基体，该正极材料基体包括Li1.2Mn0.5Ni0.2Co0.1O2。
2、制备富锂锰基正极材料
S1.将得到的正极材料基体、L-半胱氨酸和无水乙醇充分搅拌混合，将得到的混合物料利用油浴锅加热，去除无水乙醇后得到混合物料，其中，正极材料基体的质量为1g，正极材料基体与L-半胱氨酸的质量比为100：1，无水乙醇的体积为25mL，加热温度为80℃，搅拌时间为15min，搅拌速率为600rpm/min；
S2.将混合物料置于管式炉中，在氩气气氛中以350℃煅烧2h，待温度降至室温后，得到L-半胱氨酸衍生的N,S掺杂碳表面修饰富锂锰基正极材料，即富锂锰基正极材料的包覆层中包括由L-半胱氨酸热分解形成的掺杂有氮元素和硫元素的碳材料。
实施例3
1、制备正极材料基体
前驱体Ni0.2Co0.1Mn0.5(OH)2的质量为3g，按照配锂量Li：M(Ni,Co,Mn)＝1.5计算锂盐Li2CO3的质量。将称取的前驱体Ni0.2Co0.1Mn0.5(OH)2和锂盐Li2CO3在搅拌器中混合均匀，然后置于管式炉中在空气气氛中以3℃/min的升温速率升温到550℃煅烧5h，再以5℃/min的升温速率升温到900℃煅烧12h，待温度降至室温后，得到正极材料基体，该正极材料基 体包括Li1.2Mn0.5Ni0.2Co0.1O2。
2、制备富锂锰基正极材料
S1.将得到的正极材料基体、L-半胱氨酸和无水乙醇充分搅拌混合，将得到的混合物料利用油浴锅加热，去除无水乙醇后得到混合物料，其中，正极材料基体的质量为1g，正极材料基体与L-半胱氨酸的质量比为100：3，无水乙醇的体积为25mL，加热温度为80℃，搅拌时间为15min，搅拌速率为600rpm/min；
S2.将混合物料置于管式炉中，在氩气气氛中以350℃煅烧2h，待温度降至室温后，得到L-半胱氨酸衍生的N,S掺杂碳表面修饰富锂锰基正极材料，即富锂锰基正极材料的包覆层中包括由L-半胱氨酸热分解形成的掺杂有氮元素和硫元素的碳材料。
实施例4
1、制备正极材料基体
前驱体Ni0.2Co0.1Mn0.5(OH)2的质量为3g，按照配锂量Li：M(Ni,Co,Mn)＝1.5计算锂盐Li2CO3的质量。将称取的前驱体Ni0.2Co0.1Mn0.5(OH)2和锂盐Li2CO3在搅拌器中混合均匀，然后置于管式炉中在空气气氛中以3℃/min的升温速率升温到550℃煅烧5h，再以5℃/min的升温速率升温到900℃煅烧12h，待温度降至室温后，得到正极材料基体，该正极材料基体包括Li1.2Mn0.5Ni0.2Co0.1O2。
2、制备富锂锰基正极材料
S1.将得到的正极材料基体、L-半胱氨酸和无水乙醇充分搅拌混合，将得到的混合物料利用油浴锅加热，去除无水乙醇后得到混合物料，其中，正极材料基体的质量为1g，正极材料基体与L-半胱氨酸的质量比为100：0.2，无水乙醇的体积为25mL，加热温度为80℃，搅拌时间为15min，搅拌速率为600rpm/min；
S2.将混合物料置于管式炉中，在氩气气氛中以350℃煅烧2h，待温度降至室温后，得到L-半胱氨酸衍生的N,S掺杂碳表面修饰富锂锰基正极材料，即富锂锰基正极材料的包覆层中包括由L-半胱氨酸热分解形成的掺杂有氮元素和硫元素的碳材料。
实施例5
1、制备正极材料基体
前驱体Ni0.2Co0.1Mn0.5(OH)2的质量为3g，按照配锂量Li：M(Ni,Co,Mn)＝1.5计算锂盐Li2CO3的质量。将称取的前驱体Ni0.2Co0.1Mn0.5(OH)2和锂盐Li2CO3在搅拌器中混合均匀，然后置于管式炉中在空气气氛中以3℃/min的升温速率升温到550℃煅烧5h，再以5℃/min的升温速率升温到900℃煅烧12h，待温度降至室温后，得到正极材料基体，该正极材料基体包括Li1.2Mn0.5Ni0.2Co0.1O2。
2、制备富锂锰基正极材料
S1.将得到的正极材料基体、L-半胱氨酸和无水乙醇充分搅拌混合，将得到的混合物料利用油浴锅加热，去除无水乙醇后得到混合物料，其中，正极材料基体的质量为1g，正极材料基体与L-半胱氨酸的质量比为100：3.5，无水乙醇的体积为25mL，加热温度为80℃，搅拌时间为15min，搅拌速率为600rpm/min；
S2.将混合物料置于管式炉中，在氩气气氛中以350℃煅烧2h，待温度降至室温后，得到L-半胱氨酸衍生的N,S掺杂碳表面修饰富锂锰基正极材料，即富锂锰基正极材料的包覆层中包括由L-半胱氨酸热分解形成的掺杂有氮元素和硫元素的碳材料。
对比例1
富锂锰基正极材料的制备方法如下：
前驱体Ni0.2Co0.1Mn0.5(OH)2的质量为3g，按照配锂量Li：M(Ni,Co,Mn)＝1.5计算锂盐Li2CO3的质量。将称取的前驱体Ni0.2Co0.1Mn0.5(OH)2和锂盐Li2CO3在搅拌器中混合均匀，然后置于管式炉中在空气气氛中以3℃/min的升温速率升温到550℃煅烧5h，再以5℃/min的升温速率升温到900℃煅烧12h，待温度降至室温后，得到富锂锰基正极材料，该富锂锰基正极材料包括Li1.2Mn0.5Ni0.2Co0.1O2。
电化学性能测试
将实施例1～5和对比例1制备的富锂锰基正极材料制成正极片，该正极片按照富锂锰基正极材料：导电剂：PVDF＝90：5：5的质量比配料。将上述正极片组装成扣式电池，然后在电压为2.1V～4.8V，电流密度为0.05C(1C＝200mAh g-1)的条件下测试电池的首次充放电比容量和首次效率，在电流密度为0.5C(1C＝200mAh g-1)的条件下测试电池循环200周的放电比容量、容量保持率和中值电压。中值电压为电池的放电比容量的一半时所对应的电压值。此外，对扣式电池进行倍率性能测试，测试条件为：依次在0.1C、0.2C、0.5C、1C、2C、5C和0.1C的电流密度下对电池进行恒流充放电，1C＝200mAh g-1，电压为2.1V～4.8V。测试结果如表1和图1～3所示。
表1
由表1和图1～2可以看出，与对比例1相比，实施例1～5制备的富锂锰基正极材料的首次放电比容量、首次效率和循环200周的容量保持率显著较高，而循环200周的中值电压衰减较小，说明实施例1～5中掺杂有氮元素和硫元素的碳材料可有效提高富锂锰基正极材料的首次效率和循环性能，减小电压衰减。与实施例4～5相比，实施例1～3制备的富锂锰基正极材料在提升首次效率和循环性能，减小电压衰减方面的作用更明显。
由图3可以看出，与对比例1相比，实施例1～3制备的富锂锰基正极材料的倍率性能更好。实施例4～5制备的富锂锰基正极材料也进行了上述倍率性能测试，其倍率性能比对比例1好，表明实施例1～5中掺杂有氮元素和硫元素的碳材料能够有效提高富锂锰基正极材料的倍率性能。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本公开的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本公开构思的前提下，还可以做出若干变形和改进，这些都属于本公开的保护范围。因此，本公开专利的保护范围应以所附权利要求为准，说明书及附图可以用于解释权利要求的内容。
工业实用性
本公开提供的富锂锰基正极材料包括正极材料基体和包覆在正极材料基体表面的包覆层，包覆层包括掺杂有氮元素和硫元素的碳材料。上述掺杂有氮元素和硫元素的碳材料包括由含氮元素和硫元素的有机物热分解形成的掺杂有氮元素和硫元素的碳材料。本公开提供的富锂锰基正极材料能够有效提高电池的首次效率、循环性能和倍率性能，减小电压衰减，具有优异的工业实用性。

Claims (15)

  1. 一种富锂锰基正极材料，其特征在于，包括正极材料基体和包覆在所述正极材料基体表面的包覆层，所述包覆层包括掺杂有氮元素和硫元素的碳材料。
  2. 根据权利要求1所述的富锂锰基正极材料，其特征在于，所述正极材料基体包括化学式为LiaNixCoyMn0.8-x-yO2的材料，其中，1.04≤a≤1.24，0≤x≤0.2，0≤y≤0.1。
  3. 根据权利要求1～2任一项所述的富锂锰基正极材料，其特征在于，所述掺杂有氮元素和硫元素的碳材料包括由含氮元素和硫元素的有机物热分解形成的掺杂有氮元素和硫元素的碳材料。
  4. 根据权利要求3所述的富锂锰基正极材料，其特征在于，所述含氮元素和硫元素的有机物包括L-半胱氨酸和乙酰半胱氨酸中的一种或多种。
  5. 如权利要求1～4任一项所述的富锂锰基正极材料的制备方法，其特征在于，包括以下步骤：
    提供正极材料基体；
    将所述正极材料基体和所述含氮元素和硫元素的有机物混合，得到混合物料；
    将所述混合物料在保护性气氛中进行第一煅烧处理。
  6. 根据权利要求5所述的制备方法，其特征在于，所述正极材料基体和所述含氮元素和硫元素的有机物的质量比为100：(0.5～3)。
  7. 根据权利要求5所述的制备方法，其特征在于，所述正极材料基体和所述含氮元素和硫元素的有机物混合时还加入有醇类溶剂，去除所述醇类溶剂，得到所述混合物料。
  8. 根据权利要求7所述的制备方法，其特征在于，所述醇类溶剂包括乙醇、正丙醇和异丙醇中的一种或多种。
  9. 根据权利要求7所述的制备方法，其特征在于，去除所述醇类溶剂包括以下步骤：对所述正极材料基体、所述含氮元素和硫元素的有机物和所述醇类溶剂进行搅拌的同时进行加热，搅拌速度为300rpm/min～600rpm/min，加热的温度为80℃～100℃，保温的时间为15min～30min。
  10. 根据权利要求5所述的制备方法，其特征在于，所述第一煅烧处理的工艺条件包括：煅烧温度250℃～400℃，保温时间2h～3h。
  11. 根据权利要求5所述的制备方法，其特征在于，所述保护性气氛包括氩气和氮气中的一种或多种。
  12. 根据权利要求5～11任一项所述的制备方法，其特征在于，所述正极材料基体的制备方法包括以下步骤：将前驱体和锂盐混合后进行第二煅烧处理，且满足以下条件的至少 之一；
    所述前驱体包括化学式NimConMn0.8-m-n(OH)2的材料，其中，0≤m≤0.2，0≤n≤0.1；
    所述锂盐包括Li2CO3和LiOH中的一种或多种；
    所述前驱体中的金属元素与所述锂盐中的锂元素的摩尔比为1：(1.3～1.6)；
    所述第二煅烧处理的煅烧气氛包括空气和氧气中的一种或多种；
    所述第二煅烧处理的工艺条件包括：将混合后的所述前驱体和所述锂盐在450℃～600℃下煅烧4h～6h，然后在850℃～1020℃下煅烧4h～6h。
  13. 一种正极片，其特征在于，包括权利要求1～4任一项所述的富锂锰基正极材料或权利要求5～12任一项所述的制备方法制得的富锂锰基正极材料。
  14. 一种锂离子电池，其特征在于，包括权利要求13所述的正极片。
  15. 一种用电装置，其特征在于，包括权利要求14所述的锂离子电池。
PCT/CN2023/115138 2022-12-15 2023-08-28 富锂锰基正极材料及其制备方法和应用 Ceased WO2024124961A1 (zh)

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