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WO2024131093A1 - 富锂层状氧化物材料及其制备方法与应用 - Google Patents

富锂层状氧化物材料及其制备方法与应用 Download PDF

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Publication number
WO2024131093A1
WO2024131093A1 PCT/CN2023/112871 CN2023112871W WO2024131093A1 WO 2024131093 A1 WO2024131093 A1 WO 2024131093A1 CN 2023112871 W CN2023112871 W CN 2023112871W WO 2024131093 A1 WO2024131093 A1 WO 2024131093A1
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Prior art keywords
lithium
oxide material
layered oxide
rich layered
temperature
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English (en)
French (fr)
Inventor
李红磊
唐淼
张海天
吉长印
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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Priority to EP23817282.9A priority Critical patent/EP4411886A4/en
Publication of WO2024131093A1 publication Critical patent/WO2024131093A1/zh
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • 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

  • the present invention belongs to the field of battery materials, and in particular relates to a lithium-rich layered oxide material and a preparation method and application thereof.
  • Lithium-rich layered oxide 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, which has attracted extensive attention from researchers.
  • the electrochemical activation of the electrochemically inert Li2MnO3 component during the first charge process also causes the transformation of the material surface structure, which is manifested as the migration of transition metal ions, lattice dislocation, and the generation and transfer of oxygen vacancies, resulting in slow lithium ion kinetics and severe battery capacity decay.
  • the kinetics of ion transport depends largely on the main structure of the electrode material and the ion diffusion channel.
  • a stable main structure can avoid the collapse of the lattice and diffusion channel, which is conducive to the stable realization of reversible ion insertion and extraction.
  • the lithium ion insertion and extraction directions of LLO materials are parallel to the (001) crystal plane. Therefore, the material design with exposed ⁇ 010 ⁇ crystal planes, including (010), (110), (100), (0-10), (1-10) and (-100) planes, can reduce the Li insertion and extraction barrier and increase the lithium ion diffusion rate.
  • High entropy materials are a type of single-phase materials proposed in recent years that contain five or more elements and are mutually dissolved in equimolar or near molar ratios. They exhibit unique effects in thermodynamics, kinetics, microstructure and performance, namely high entropy effect, hysteresis diffusion effect, lattice distortion effect, etc. Therefore, combining the component design advantages of high entropy materials, optimizing the structural characteristics of LLO layered materials, and developing high Lithium battery positive electrode materials with high rate and long life are of great significance.
  • the object of the present invention is to provide a lithium-rich layered oxide material and a preparation method and application thereof.
  • the ⁇ 010 ⁇ crystal plane of the lithium-rich layered oxide material provided by the present invention is exposed over a large area, and when used as a positive electrode material for a lithium battery, it has higher rate performance and cycle life.
  • the present invention provides a lithium-rich layered oxide material, wherein the primary particles of the lithium-rich layered oxide material are polyhedrons with exposed ⁇ 010 ⁇ crystal planes, and the area of the ⁇ 010 ⁇ crystal planes accounts for more than 20%.
  • the area of the ⁇ 010 ⁇ crystal plane is 30-45%.
  • the configuration entropy value of the lithium-rich layered oxide material is 6.0 to 9.0.
  • the present invention provides a method for preparing a lithium-rich layered oxide material, comprising the following steps:
  • preparing a manganese nickel cobalt hydroxide precursor mixing the manganese nickel cobalt hydroxide precursor, a lithium source compound, a sodium source compound and an M source compound, and calcining under oxygen conditions to obtain a lithium-rich layered oxide material;
  • M in the M source compound is one or more of Mg, B, Al, Ti, Zr, Nb, Mo and W;
  • the primary particles of the lithium-rich layered oxide material are polyhedrons with exposed ⁇ 010 ⁇ crystal planes, and the area of the ⁇ 010 ⁇ crystal planes accounts for more than 20%.
  • the specific steps of preparing the manganese nickel cobalt hydroxide precursor include:
  • the specific steps satisfy at least one of the following conditions:
  • the soluble salt of manganese is one or more of manganese sulfate, manganese chloride and manganese nitrate;
  • the soluble salt of nickel is one or more of nickel sulfate, nickel chloride and nickel nitrate;
  • the soluble salt of cobalt is one or more of cobalt sulfate, cobalt chloride and cobalt nitrate;
  • the complexing agent is one or more of ammonia water, ethylenediaminetetraacetic acid and ethylenediamine;
  • the total concentration of metal ions in the mixed salt solution is 1 to 3 mol/L;
  • the sodium hydroxide is mixed in the form of a sodium hydroxide aqueous solution, and the concentration of the sodium hydroxide aqueous solution is 0.5 to 3 mol/L;
  • the complexing agent is mixed in the form of a complexing agent aqueous solution, and the concentration of the complexing agent aqueous solution is 1 to 10 mol/L;
  • the stirring rate of the complexation and precipitation reaction is 200-800 r/min;
  • the temperature of the complexation and precipitation reaction is 30 to 70°C;
  • the time of the complexation and precipitation reaction is 10 to 50 hours.
  • the lithium source compound is one or more of LiOH, Li 2 CO 3 , Li 2 SO 4 , LiCl and LiNO 3 ;
  • the sodium source compound is Na 2 CO 3 and/or NaHCO 3 ;
  • the M source compound is one or more of M oxide, M hydroxide, M carbonate and M sulfate.
  • the roasting method is step-by-step roasting, and the specific process includes:
  • the first calcination temperature is 300-600°C; the heating rate to the first calcination temperature is 1-5°C/min; the time of the first heat preservation calcination is 2-8h;
  • the second calcination temperature is 800-1000°C; the heating rate to the second calcination temperature is 1-5°C/min; the secondary heat preservation calcination time is 10-20h;
  • oxygen-containing gas is continuously introduced into the roasting equipment.
  • the oxygen-containing gas feed rate in step i) is 0.5-5 m 3 /h
  • the oxygen-containing gas feed rate in step ii) is 0.5-5 m 3 /h.
  • the present invention provides a lithium-ion secondary battery, wherein the positive electrode material of the lithium-ion secondary battery comprises the lithium-rich layered oxide material described in the above technical solution or the positive electrode material prepared by the preparation method described in the above technical solution. Lithium-rich layered oxide materials.
  • the present invention provides an electric device, wherein the electric device is equipped with the lithium-ion secondary battery described in the above technical solution.
  • the present invention provides a lithium-rich layered oxide material and its preparation method and application.
  • the primary particles of the lithium-rich layered oxide material provided by the present invention are polyhedrons with exposed ⁇ 010 ⁇ crystal planes, and the area of the ⁇ 010 ⁇ crystal plane accounts for >20%.
  • the present invention improves the system configuration entropy by introducing a high-entropy component design of multiple cations in the LLO material, thereby providing the material with high structural stability and stable ion diffusion channels; at the same time, the change in entropy further affects the thermodynamically stable structure and crystal plane energy of the system, achieves local minimization of Gibbs free energy, induces the exposure of the ⁇ 010 ⁇ crystal plane with a lithium ion fast transmission channel, and makes the area of the ⁇ 010 ⁇ crystal plane account for >20%, providing more channels for rapid ion migration and improving electrode reaction kinetics.
  • the lithium-rich layered oxide material provided by the present invention has high rate performance and long cycle stability when used as a positive electrode material for lithium batteries, and has good application prospects in the field of lithium secondary battery production and manufacturing.
  • FIG1 is an XRD diagram of the lithium-rich layered oxide material of Example 1 provided by the present invention.
  • FIG2 is a HRTEM image and a fast Fourier transform image of the lithium-rich layered oxide material of Example 1 provided by the present invention
  • FIG3 is a SEM image of the lithium-rich layered oxide material and a schematic diagram of the primary particle structure of Example 1 provided by the present invention
  • FIG4 is a comparison chart of the cycle performance of the oxide materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 provided by the present invention in a lithium secondary battery test;
  • FIG5 is a comparison chart of the rate performance of the oxide materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 provided by the present invention in a lithium secondary battery test.
  • the present invention provides a lithium-rich layered oxide material and its preparation method and application.
  • the core technical problem to be solved is that the irreversible phase change of LLO materials and the structural distortion and transition metal ion rearrangement caused by the anion redox reaction lead to slow lithium ion transmission kinetics, severe battery capacity decay and voltage decay.
  • the present invention improves the system configuration entropy through the high entropy component design of multiple cations, providing high structural stability and stable ion diffusion channels for LLO materials; at the same time, the change in entropy will affect the energy of the system and crystal plane, realize the local minimization of Gibbs free energy, induce the exposure of the ⁇ 010 ⁇ crystal plane with a fast lithium ion transmission channel, and the area of the ⁇ 010 ⁇ crystal plane accounts for >20%, providing more channels for rapid ion migration and improving electrode reaction kinetics.
  • the present invention forms a high-entropy solid solution through a multi-cation component design.
  • This component design can increase the system configuration entropy and induce the exposure of the ⁇ 010 ⁇ crystal plane with a fast lithium ion transmission channel, thereby improving the electrochemical properties of the material; while the traditional single metal ion or multi-metal ion doping uses a higher metal-oxygen bond energy to improve the stability of the crystal structure and achieve improved electrochemical properties of the material.
  • the configuration entropy (Sconfig) in a multi-component material system mainly depends on the types of elements and their molar fractions, which can be quantified according to the following formula:
  • xi and xj are the mole fractions of cations and anions, respectively, and R is the gas constant.
  • ⁇ 0 is the surface energy of the material at 0K
  • A is the Helmholtz free energy
  • T is the temperature
  • the surface energy of a system with simple components and low entropy is mainly affected by temperature, while the surface energy of a system with many components and high entropy is mainly affected by configurational entropy; the present invention achieves large-area exposure of specific ⁇ 010 ⁇ crystal planes through the regulation of multi-cation high-entropy components, thereby improving the stability of the electrode material structure and the electrochemical performance.
  • the present invention specifically proposes the following technical solutions:
  • the present invention provides a lithium-rich layered oxide material, wherein the primary particles of the lithium-rich layered oxide material are polyhedrons with exposed ⁇ 010 ⁇ crystal planes, and the area of the ⁇ 010 ⁇ crystal planes accounts for >20%, preferably 30-45%, more preferably 35-40%, and specifically 36.4%, 37.0%, 37.2%, 37.5%, 37.4% or 38.3%.
  • the configuration entropy value of the lithium-rich layered oxide material is preferably 6.0 to 9.0, specifically 6.0, 6.71, 7.45, 7.48, 7.80, 7.89, 8.85 or 9.0.
  • the chemical formula of the lithium-rich layered oxide material is specifically any one of the following chemical formulas: Li(Li 0.18 Na 0.02 Ni 0.1552 Co 0.0776 Mn 0.5432 Al 0.008 Ti 0.016 )O 2 ; Li(Li 0.14 Na 0.01 Ni 0.20825 Co 0.12495 Mn 0.4998 Zr 0.0170 )O 2 ; Li(Li 0.14 Na 0.01 Ni 0.206125 Co 0.123675 Mn 0.4947 Mg 0.0085 Ti 0.017 )O 2 ; Li(Li 0.19 Na 0.01 Ni 0.20825 Co 0.20825 Mn 0.4165 Ti 0.0085 Zr 0.0085 )O 2 ; Li(Li 0.09 Na 0.01 Ni 0.2205 Co 0.2205 Mn 0.441 Nb 0.009 Mo 0.009 )O 2 ; Li(Li 0.18 Na 0.02 Ni 0.1568 Co 0.1568 Mn 0.4704 Zr 0.008 Ti 0.008 )O 2 ; Li(Li 0.18 Na 0.02 Ni 0.1568
  • the present invention also provides a method for preparing the lithium-rich layered oxide material described in the above technical solution, comprising the following steps:
  • preparing a manganese nickel cobalt hydroxide precursor mixing the manganese nickel cobalt hydroxide precursor, a lithium source compound, a sodium source compound and an M source compound, and calcining under oxygen conditions to obtain a lithium-rich layered oxide material;
  • M in the M source compound is one or more of Mg, B, Al, Ti, Zr, Nb, Mo and W;
  • the primary particles of the lithium-rich layered oxide material are polyhedrons with exposed ⁇ 010 ⁇ crystal planes, and the area of the ⁇ 010 ⁇ crystal planes accounts for more than 20%.
  • the specific steps of preparing the manganese nickel cobalt hydroxide precursor include:
  • the soluble salt of manganese is preferably one or more of manganese sulfate, manganese chloride and manganese nitrate;
  • the soluble salt of nickel is preferably one or more of nickel sulfate, nickel chloride and nickel nitrate;
  • the soluble salt of cobalt is preferably one or more of cobalt sulfate, cobalt chloride and cobalt nitrate;
  • the total concentration of metal ions in the mixed salt solution is preferably 1-3 mol/L, specifically 1 mol/L, 1.5 mol/L, 1.8 mol/L, 2 mol/L, 2.5 mol/L or 3 mol/L.
  • the sodium hydroxide is preferably mixed in the form of a sodium hydroxide aqueous solution, and the concentration of the sodium hydroxide aqueous solution is preferably 0.5-3 mol/L, specifically 0.5 mol/L, 1 mol/L, 1.5 mol/L, 2 mol/L, 2.5 mol/L or 3 mol/L;
  • the complexing agent is preferably one or more of ammonia water, ethylenediaminetetraacetic acid (EDTA) and ethylenediamine;
  • the complexing agent is mixed in the form of a complexing agent aqueous solution, and the complexing agent ...
  • the concentration of the aqueous solution of the agent is preferably 1-10 mol/L, specifically 1 mol/L, 1.5 mol/L, 2 mol/L, 2.5 mol/L, 3 mol/L, 3.5 mol/L, 4 mol/L, 4.5 mol/L, 5 mol/L, 5.5 mol/L, 6 mol/L, 6.5 mol/L, 7.5 mol/L, 8 mol/L, 8.5 mol/L, 9 mol/L, 9.5 mol/L or 10 mol/L; the mixing is preferably carried out in a reactor added with water as a base liquid.
  • the pH value of the mixed system can be maintained at 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12, 12.1, 12.2, 12.3, 12.4, 12.5, 12.7, 12.8, 12.9 or 13;
  • the stirring rate of the complexation and precipitation reaction is preferably 200-800 r/min, specifically 200 r/min, 250 r/min, 300 r/min, 350 r/min, 400 r/min, 450 r/min , 500r/min, 550r/min, 600r/min, 650r/min, 700r/min, 750r/min or 800r/min;
  • the temperature of the complexation and precipitation reaction is preferably 30-70°C, specifically 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 56°C, 60°
  • the drying temperature is preferably 100-300°C, specifically 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C or 300°C.
  • the lithium source compound is preferably one or more of LiOH, Li 2 CO 3 , Li 2 SO 4 , LiCl and LiNO 3 ;
  • the sodium source compound is preferably Na 2 CO 3 and/or NaHCO 3 ;
  • the M source compound is preferably one or more of M oxide, M hydroxide, M carbonate and M sulfate.
  • the aerobic condition is preferably an air atmosphere or a pure oxygen atmosphere
  • the calcination method is preferably a step-by-step calcination, and the specific process includes:
  • the first roasting temperature is preferably 300-600°C, specifically 300°C, 320°C, 350°C, 370°C, 400°C, 420°C, 450°C, 470°C, 500°C, 520°C, 550°C, 570°C or 600°C;
  • the heating rate to the first roasting temperature is preferably 1-5°C/min, specifically 1°C/min, 1.5°C/min, 2°C/min, 2.5°C/min, 3°C/min, 3.5°C/min, 4°C/min, 4.5°C/min or 5°C/min;
  • the time for the one-time heat preservation roasting is preferably 2-8h, specifically 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8h.
  • the second calcination temperature is preferably 800-1000°C, specifically 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, 860°C, 870°C, 880°C, 890°C, 900°C, 910°C, 920°C, 930°C, 940°C, 950°C, 960°C, 970°C, 980°C, 990°C or 1000°C;
  • the heating rate to the second calcination temperature is preferably 1-5°C/min, specifically 1°C/min, 1.5°C/min, 2°C/min, 2.5°C/min, 3°C/min, 3.5°C/min, 4°C/min, 4.5°C/min or 5°C/min;
  • the time of the secondary heat preservation roasting is preferably 10-20h, specifically 10h, 10.5h, 11h, 11.5h, 12h, 12.5h,
  • the aerobic condition is preferably achieved by continuously introducing oxygen-containing gas into the roasting equipment used; wherein, the oxygen-containing gas intake rate of step i) is preferably 0.5-5m 3 /h, specifically 0.5m 3 /h, 1m 3 /h, 1.5m 3 /h, 2m 3 /h, 2.5m 3 /h, 3m 3 /h, 3.5m 3 /h, 4m 3 /h, 4.5m 3 /h or 5m 3 /h; the oxygen-containing gas intake rate of step ii) is preferably 0.5-5m 3 /h, specifically 0.5m 3 /h, 1m 3 /h, 1.5m 3 /h, 2m 3 /h, 2.5m 3 /h, 3m 3 /h, 3.5m 3 /h, 4m 3 /h, 4.5m 3 /h or 5m 3 /h.
  • the obtained product is preferably cooled, then crushed and sieved.
  • the present invention also provides a lithium-ion secondary battery, comprising a positive electrode, a negative electrode, an electrolyte and a separator between the positive electrode and the negative electrode; wherein the material of the positive electrode comprises the lithium-rich layered oxide material described in the above technical solution or the lithium-rich layered oxide material prepared by the preparation method described in the above technical solution.
  • the present invention also provides an electrical device, wherein the electrical device is equipped with the lithium-ion secondary battery described in the above technical solution.
  • the stirring speed of the mixed solution in the reactor was set to 400 r/min, the reaction temperature was 55°C, and after the reaction was continued for 36 hours, the obtained precipitate was discharged, washed with deionized water and dried at a drying temperature of 150°C to obtain a manganese nickel cobalt hydroxide precursor P.
  • the mixture Q is placed in an air atmosphere furnace for two-step calcination, the specific process is: firstly, the furnace temperature is increased from room temperature to 550°C at a heating rate of 3°C/min, and the mixture is calcined at this temperature for 4 hours, and air is continuously introduced into the furnace during the heating and heat-insulating calcination, with an air intake rate of 2.5m3 /h; then, the furnace temperature is further increased to 900°C at a heating rate of 3°C/min, and the mixture is calcined at this temperature for 12 hours, and air is continuously introduced into the furnace during the heating and heat-insulating calcination, with an air intake rate of 2.5m3 /h.
  • the product was cooled in the furnace, and then crushed and sieved to obtain lithium-rich layered oxide material Li(Li 0.18 Na 0.02 Ni 0.1552 Co 0.0776 Mn 0.5432 Al 0.008 Ti 0.016 )O 2 .
  • the lithium-rich layered oxide material prepared in this embodiment was characterized by X-ray diffraction (XRD), and the result is shown in Figure 1, which is an XRD diagram of the lithium-rich layered oxide material of Example 1 provided by the present invention. It can be seen from Figure 1 that, except for the weaker diffraction peak of the monoclinic structure belonging to the C2/m space point group between 20° and 25°, the remaining diffraction peaks of the material can correspond to the hexagonal layered structure, indicating that the multi-component design has not changed the bulk structure characteristics of the material.
  • XRD X-ray diffraction
  • the lithium-rich layered oxide material prepared in this embodiment is characterized by high-resolution transmission electron microscopy (HRTEM), and a fast Fourier transform spectrum is drawn.
  • HRTEM high-resolution transmission electron microscopy
  • Figure 2 is an HRTEM image and a fast Fourier transform image of the lithium-rich layered oxide material of Example 1 provided by the present invention, wherein the left image is an HRTEM image and the right image is a fast Fourier transform spectrum.
  • the interplanar spacing of the material is 0.47nm, which matches the (003) crystal plane of the hexagonal phase and the (001) crystal plane of the monoclinic lithium-rich component; the fast Fourier transform image proves that the top exposed crystal plane of the material is the (003) crystal plane.
  • the lithium-rich layered oxide material prepared in this embodiment was observed by scanning electron microscopy (SEM), and a schematic diagram of the structure of its primary particles was drawn.
  • SEM scanning electron microscopy
  • Figure 3 is a SEM image and a schematic diagram of the structure of the primary particles of the lithium-rich layered oxide material in Example 1 provided by the present invention, wherein the left image is a SEM image and the right image is a schematic diagram of the structure of the primary particles.
  • the material is agglomerated by polyhedrons with a diameter of about 1 ⁇ m; it can be seen from the right image in Figure 3 that the top exposed crystal plane of the primary particle of the material is the ⁇ 001 ⁇ crystal plane, and the side is the ⁇ 010 ⁇ crystal plane.
  • the atomic arrangement of the ⁇ 010 ⁇ crystal plane is an open structure, which is conducive to the transport of lithium ions.
  • the stirring speed of the mixed solution in the reactor was set to 600 r/min, the reaction temperature was 50°C, and after the reaction was continued for 36 hours, the obtained precipitate was discharged, washed with deionized water and dried at a drying temperature of 160°C to obtain a manganese-nickel-cobalt hydroxide precursor P.
  • the mixture Q is placed in an oxygen atmosphere furnace for two-step calcination, the specific process being: firstly, the furnace temperature is increased from room temperature to 500°C at a heating rate of 2.5°C/min, and the mixture is calcined at this temperature for 6 hours, during which oxygen is continuously introduced into the furnace at a rate of 3m3 /h; then, the furnace temperature is further increased to 880°C at a heating rate of 2.5°C/min, and the mixture is calcined at this temperature for 10 hours, during which oxygen is continuously introduced into the furnace at a rate of 3m3 /h.
  • the stirring speed of the mixed solution in the reactor was set to 500 r/min, the reaction temperature was 60°C, and after the reaction was continued for 40 hours, the obtained precipitate was discharged, washed with deionized water and dried at a drying temperature of 180°C to obtain a manganese-nickel-cobalt hydroxide precursor P.
  • the mixture Q is placed in an oxygen atmosphere furnace for two-step calcination, the specific process being: firstly, the furnace temperature is increased from room temperature to 550°C at a heating rate of 4°C/min, and calcined at this temperature for 5 hours, oxygen is continuously introduced into the furnace during the heating and heat-insulating calcination, and the air intake rate is 5m3 /h; then, the furnace temperature is further increased to 920°C at a heating rate of 4°C/min, and calcined at this temperature for 12 hours, oxygen is continuously introduced into the furnace during the heating and heat-insulating calcination, and the air intake rate is 5m3 /h.
  • lithium-rich layered oxide material Li(Li 0.14 Na 0.01 Ni 0.206125 Co 0.123675 Mn 0.4947 Mg 0.0085 Ti 0.017 )O 2 .
  • the stirring speed of the mixed solution in the reactor was set to 600 r/min, and the reaction temperature was 65°C. After the reaction was continued for 45 hours, the obtained precipitate was discharged, washed with deionized water and dried at a drying temperature of 160°C to obtain a manganese nickel cobalt hydroxide precursor P.
  • the mixture Q is placed in an air atmosphere furnace for two-step calcination, the specific process is: firstly, the furnace temperature is increased from room temperature to 600°C at a heating rate of 2°C/min, and the mixture is calcined at this temperature for 4 hours, and air is continuously introduced into the furnace during the heating and heat-insulating calcination, with an air intake rate of 3m3 /h; then, the furnace temperature is further increased to 950°C at a heating rate of 2°C/min, and the mixture is calcined at this temperature for 10 hours, and air is continuously introduced into the furnace during the heating and heat-insulating calcination, with an air intake rate of 3m3 /h.
  • lithium-rich layered oxide material Li(Li 0.19 Na 0.01 Ni 0.20825 Co 0.20825 Mn 0.4165 Ti 0.0085 Zr 0.0085 )O 2 .
  • the mixture Q is placed in an oxygen atmosphere furnace for two-step calcination, the specific process being: firstly, the furnace temperature is increased from room temperature to 600°C at a heating rate of 4°C/min, and the mixture is calcined at this temperature for 3 hours, during which oxygen is continuously introduced into the furnace at a rate of 2m3 /h; then, the furnace temperature is further increased to 980°C at a heating rate of 4°C/min, and the mixture is calcined at this temperature for 15 hours, during which oxygen is continuously introduced into the furnace at a rate of 2m3 /h.
  • the product was cooled in the furnace, and then crushed and sieved to obtain lithium-rich layered oxide material Li(Li 0.09 Na 0.01 Ni 0.2205 Co 0.2205 Mn 0.441 Nb 0.009 Mo 0.009 )O 2 .
  • the stirring speed of the mixed solution in the reactor was set to 600 r/min, and the reaction temperature was 55°C. After the reaction was continued for 50 hours, the obtained precipitate was discharged, washed with deionized water and dried at a drying temperature of 160°C to obtain a manganese-nickel-cobalt hydroxide precursor P.
  • the mixture Q is placed in an air atmosphere furnace for two-step calcination, the specific process is: firstly, the furnace temperature is increased from room temperature to 550°C at a heating rate of 3°C/min, and the mixture is calcined at this temperature for 6 hours. During the heating and heat-insulating calcination, air is continuously introduced into the furnace at a rate of 3m3 /h; then, the furnace temperature is further increased to 960°C at a heating rate of 3°C/min, and the mixture is calcined at this temperature for 12 hours. During the heating and heat-insulating calcination, air is continuously introduced into the furnace at a rate of 3m3 /h.
  • the product was cooled in the furnace, and then crushed and sieved to obtain lithium-rich layered oxide material Li(Li 0.18 Na 0.02 Ni 0.1568 Co 0.1568 Mn 0.4704 Zr 0.008 Ti 0.008 )O 2 .
  • the stirring speed of the mixed solution in the reactor was set to 750 r/min, the reaction temperature was 56°C, and after the reaction was continued for 42 hours, the obtained precipitate was discharged, washed with deionized water and dried at a drying temperature of 160°C to obtain a manganese nickel cobalt hydroxide precursor P.
  • the mixture Q is placed in an oxygen atmosphere furnace for two-step calcination, the specific process is: firstly, the furnace temperature is increased from room temperature to 580°C at a heating rate of 3°C/min, and the mixture is calcined at this temperature for 6 hours, and oxygen is continuously introduced into the furnace during the heating and heat-insulating calcination, and the air intake rate is 5m3 /h; then, the furnace temperature is further increased to 920°C at a heating rate of 3°C/min, and the mixture is calcined at this temperature for 18 hours, and oxygen is continuously introduced into the furnace during the heating and heat-insulating calcination, and the air intake rate is 5m3 /h.
  • the product was cooled in the furnace, and then crushed and sieved to obtain lithium-rich layered oxide material Li(Li 0.14 Na 0.01 Ni 0.1649 Co 0.1649 Mn 0.4947 Al 0.0085 Zr 0.017 )O 2 .
  • the stirring speed of the mixed solution in the reactor is set to 400r/min, and the reaction temperature is 55°C. After the reaction is continued for 36 hours, the obtained precipitate is discharged, washed with deionized water and dried at a drying temperature of 150°C to obtain a manganese nickel cobalt hydroxide precursor P.
  • the mixture Q is placed in an air atmosphere furnace for two-step calcination, the specific process being: firstly, the furnace temperature is increased from room temperature to 550°C at a heating rate of 3°C/min, and calcined at this temperature for 4 hours, and air is continuously introduced into the furnace during the heating and heat-insulating roasting process, with an air intake rate of 2.5m3 /h; then, the furnace temperature is further increased to 900°C at a heating rate of 3°C/min, and calcined at this temperature for 12 hours, and air is continuously introduced into the furnace during the heating and heat-insulating roasting process, with an air intake rate of 2.5m3 /h.
  • the product was cooled in the furnace, and then crushed and sieved to obtain lithium-rich layered oxide material Li(Li 0.2 Ni 0.16 Co 0.08 Mn 0.56 )O 2 .
  • Mixture A was pumped into the spray drying equipment through a peristaltic pump, the liquid inlet rate was set to 0.8 L/min, the spray drying inlet temperature was set to 250°C, the outlet temperature was set to 120°C, and the carrier gas rate was set to 50 L/min.
  • the liquid in the mixture evaporated at high temperature to obtain powder B with uniformly mixed metal ions.
  • the powder B was placed in an air atmosphere furnace for two-step calcination, the specific process being: firstly, the furnace temperature was increased from room temperature to 550°C at a heating rate of 3°C/min, and calcined at this temperature for 4 hours, and air was continuously introduced into the furnace during the heating and heat-insulating calcination process at a rate of 2.5 m3 /h; then, the furnace temperature was further increased to 900°C at a heating rate of 3°C/min, and calcined at this temperature for 12 hours, and air was continuously introduced into the furnace during the heating and heat-insulating calcination process at a rate of 2.5 m3 /h.
  • the product was cooled in the furnace, and then crushed and sieved to obtain lithium-rich layered oxide material Li(Li 0.18 Na 0.02 Ni 0.1552 Co 0.0776 Mn 0.5432 Al 0.008 Ti 0.016 )O 2 .
  • the electrochemical performance of the oxide materials prepared in Examples 1 to 7 and Comparative Examples 1 to 2 as positive electrode materials of lithium secondary batteries was tested in button-type lithium secondary batteries.
  • the specific preparation method of the lithium secondary battery and its positive electrode sheet was as follows: the prepared positive electrode material powder was mixed with acetylene black and polyvinylidene fluoride in a mass ratio of 90:5:5, an appropriate amount of N-methylpyrrolidone was added as a dispersant, and the mixture was ground into a slurry; then the slurry was evenly coated on an aluminum foil, vacuum dried at 120° C.
  • the dried electrode sheet was rolled with a roller mill, and the aluminum foil was cut with a slicer into a circular electrode sheet with a diameter of 1.3 cm, and the loading amount of the active material was controlled to be about 10 mg/cm 2 ; a half-cell was assembled in an argon atmosphere glove box, the water partial pressure was ⁇ 0.1 ppm, and the oxygen partial pressure was ⁇ 0.1 ppm; metallic lithium was used as the counter electrode, and 1M LiPF 6
  • the (FEC/EC/DMC, volume ratio of 1:1:1) solution is the electrolyte, the assembly specification is CR2032 button battery, and the constant current charge and discharge mode is used for charge and discharge at room temperature.
  • the voltage range is 2.0-4.65V, and the current density is 50mA/g (0.2C rate) for 100 charge and discharge cycles; the lithium ion diffusion coefficients of different materials are compared by electrochemical impedance spectroscopy (EIS) test, and the test frequency range is 100kHz-0.01Hz; the battery rate performance test current density is 50mA/g, 500mA/g, 1250mA/g, 2500mA/g correspond to 0.2C, 2C, 5C, 10C respectively.
  • EIS electrochemical impedance spectroscopy
  • FIG4 is a comparison diagram of the cycle performance of the oxide materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 provided by the present invention in the lithium secondary battery test;
  • the first week charge specific capacity, first week discharge specific capacity, first week coulomb efficiency, capacity retention rate after 100 weeks and lithium ion diffusion coefficient data of the oxide materials prepared in Examples 1 to 7 and Comparative Examples 1 to 2 in the lithium secondary battery test are shown in Table 2:
  • FIG5 is a comparison chart of the rate performance of the oxide materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 provided by the present invention in the lithium secondary battery test;
  • the rate performance data of the oxide materials prepared in Examples 1 to 7 and Comparative Examples 1 to 2 in the lithium secondary battery test are shown in Table 3:

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Abstract

一种富锂层状氧化物材料及其制备方法与应用，该富锂层状氧化物材料的一次颗粒为{010}晶面暴露的多面体，且{010}晶面的面积占比﹥20％，通过在LLO材料中引入多种阳离子的高熵组分设计，提高了系统构型熵，为材料提供了高的结构稳定性和稳定的离子扩散通道。该富锂层状氧化物材料作为锂电池正极材料使用时具有高的倍率性能与长的循环稳定性。

Description

富锂层状氧化物材料及其制备方法与应用
本申请要求于2022年12月20日提交中国专利局、申请号为202211638986.6、发明名称为“一种富锂层状氧化物材料及其制备方法与应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于电池材料领域，尤其涉及一种富锂层状氧化物材料及其制备方法与应用。
背景技术
近年来新能源汽车的快速发展对锂二次电池的能量密度、循环寿命和功率密度提出了更高的要求，而正极材料是锂二次电池性能突破的关键因素。富锂层状氧化物正极材料(LLO)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。但是，首次充电过程中电化学惰性Li2MnO3组分的电化学活化，在带来高容量和能量密度的同时，也引起材料表面结构的转变，表现为过渡金属离子的迁移、晶格错位、氧空位的产生与转移，导致缓慢的锂离子动力学和严重的电池容量衰减。
通常而言，离子传输动力学很大程度上取决于电极材料的主体结构和离子扩散通道。稳定的主体结构可以避免晶格和扩散通道的坍塌，有利于稳定实现可逆的离子嵌入与脱出。和传统层状正极材料一样，LLO材料的锂离子脱嵌方向均沿平行于(001)晶面方向，因此具有暴露的{010}晶面的材料设计，包括(010)、(110)、(100)、(0-10)、(1-10)和(-100)平面，可以降低Li脱嵌势垒，提高锂离子扩散速度。然而，相关研究表明LLO材料中{010}晶面表面能较高，生长速度大于低表面能晶面，最终在晶体生长过程中消失。因此，特殊优势晶面暴露的LLO材料的合成依旧是一个难点。
高熵材料，是近年来提出的一类含有5种及以上元素，并以等摩尔或近摩尔比相互固溶而得到的单一相材料，在热力学、动力学、微观结构和性能等方面表现出独特的效应，即高熵效应、迟滞扩散效应、晶格畸变效应等。因此，结合高熵材料的组分设计优势，优化LLO层状材料的结构特征，开发具有高 倍率、长寿命的锂电池正极材料，具有十分重要的意义。
发明内容
有鉴于此，本发明的目的在于提供一种富锂层状氧化物材料及其制备方法与应用，本发明提供的富锂层状氧化物材料的{010}晶面大面积暴露，作为锂电池正极材料使用时具有较高的倍率性能和循环寿命。
本发明提供了一种富锂层状氧化物材料，所述富锂层状氧化物材料的一次颗粒为{010}晶面暴露的多面体，且{010}晶面的面积占比>20％。
优选的，所述{010}晶面的面积占为30～45％。
优选的，所述富锂层状氧化物材料的构型熵值为6.0～9.0。
优选的，所述富锂层状氧化物材料的化学式为Li(LiaNabMncNidCoeMf)O2，其中，M为Mg、B、Al、Ti、Zr、Nb、Mo和W中的一种或多种，0<a≤0.3，0<b≤0.05，0.4<c≤0.7，d＞0，e＞0，f＞0，且a+b+c+d+e+f＝1。
本发明提供了一种富锂层状氧化物材料的制备方法，包括以下步骤：
制备锰镍钴氢氧化物前驱体，将所述锰镍钴氢氧化物前驱体、锂源化合物、钠源化合物和M源化合物混合，在有氧条件下焙烧，得到富锂层状氧化物材料；
所述M源化合物中的M为Mg、B、Al、Ti、Zr、Nb、Mo和W中的一种或多种；
所述富锂层状氧化物材料的一次颗粒为{010}晶面暴露的多面体，且{010}晶面的面积占比>20％。
优选的，所述制备锰镍钴氢氧化物前驱体的具体步骤包括：
a)将锰的可溶性盐、镍的可溶性盐、钴的可溶性盐和水混合，得到混合盐溶液；
b)将所述混合盐溶液、氢氧化钠和络合剂混合，并控制所述氢氧化钠和络合剂的用量使混合体系的pH值维持在10～13进行络合与沉淀反应，得到沉淀物；
c)将所述沉淀物进行洗涤和干燥，得到锰镍钴氢氧化物前驱体。
优选的，所述具体步骤满足以下条件中的至少一个条件：
所述锰的可溶性盐为锰的硫酸盐、锰的氯化物和锰的硝酸盐中的一种或多种；
所述镍的可溶性盐为镍的硫酸盐、镍的氯化物和镍的硝酸盐中的一种或多种；
所述钴的可溶性盐为钴的硫酸盐、钴的氯化物和钴的硝酸盐中的一种或多种；
所述络合剂为氨水、乙二胺四乙酸和乙二胺中的一种或多种；
所述混合盐溶中金属离子的总浓度为1～3mol/L；
所述氢氧化钠以氢氧化钠水溶液的形式参与混合，所述氢氧化钠水溶液的浓度为0.5～3mol/L；
所述络合剂以络合剂水溶液的形式参与混合，所述络合剂水溶液的浓度为1～10mol/L；
所述络合与沉淀反应的搅拌速率为200～800r/min；
所述络合与沉淀反应的温度为30～70℃；
所述络合与沉淀反应的时间为10～50h。
优选的，所述锂源化合物为LiOH、Li2CO3、Li2SO4、LiCl和LiNO3中的一种或多种；所述钠源化合物为Na2CO3和/或NaHCO3；所述M源化合物为M的氧化物、M的氢氧化物、M的碳酸盐和M的硫酸盐中的一种或多种。
优选的，所述焙烧的方式为分步焙烧，具体过程包括：
i)从环境温度升温至第一焙烧温度，进行一次保温焙烧；
所述第一焙烧温度为300～600℃；升温至所述第一焙烧温度的升温速率为1～5℃/min；所述一次保温焙烧的时间为2～8h；
ii)继续升温至第二焙烧温度，进行二次保温焙烧；
所述第二焙烧温度为800～1000℃；升温至所述第二焙烧温度的升温速率为1～5℃/min；所述二次保温焙烧的时间为10～20h；
焙烧过程中，持续向所用焙烧设备中通入含氧气体，步骤i)的含氧气体进气速率为0.5～5m3/h，步骤ii)的含氧气体进气速率为0.5～5m3/h。
本发明提供了一种锂离子二次电池，所述锂离子二次电池的正极材料包括上述技术方案所述的富锂层状氧化物材料或上述技术方案所述制备方法制得 的富锂层状氧化物材料。
本发明提供了一种用电装置，所述用电装置安装有上述技术方案所述的锂离子二次电池。
与现有技术相比，本发明提供了一种富锂层状氧化物材料及其制备方法与应用。本发明提供的富锂层状氧化物材料的一次颗粒为{010}晶面暴露的多面体，且{010}晶面的面积占比>20％。本发明通过在LLO材料中引入多种阳离子的高熵组分设计，提高了系统构型熵，从而为材料提供了高的结构稳定性和稳定的离子扩散通道；同时，熵的变化进一步影响体系热力学稳定结构和晶面能量，实现吉布斯自由能的局部最小化，诱导具有锂离子快速传输通道的{010}晶面的暴露，使{010}晶面的面积占比>20％，为离子快速迁移提供了更多通道，提高电极反应动力学。本发明提供的富锂层状氧化物材料作为锂电池正极材料使用时具有高的倍率性能与长的循环稳定性，其在锂二次电池生产制造领域具有良好的应用前景。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1为本发明提供的实施例1富锂层状氧化物材料的XRD图；
图2为本发明提供的实施例1富锂层状氧化物材料的HRTEM及其快速傅里叶变换图；
图3为本发明提供的实施例1富锂层状氧化物材料的SEM图与一次颗粒结构示意图；
图4为本发明提供的实施例1、对比例1与对比例2所制备的氧化物材料在锂二次电池测试中的循环性能对比图；
图5为本发明提供的实施例1、对比例1与对比例2所制备的氧化物材料在锂二次电池测试中的倍率性能对比图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
为了克服现有LLO材料的缺陷，本发明提供了一种富锂层状氧化物材料及其制备方法与应用，其所要解决的核心技术问题在于：LLO材料不可逆的相变和阴离子氧化还原反应引起的结构扭曲和过渡金属离子重排，导致缓慢的锂离子传输动力学，严重的电池容量衰减和电压衰减。为此，本发明通过多种阳离子的高熵组分设计，提高了系统构型熵，为LLO材料提供高的结构稳定性和稳定的离子扩散通道；同时，熵的变化会影响体系和晶面的能量，实现吉布斯自由能的局部最小化，诱导具有锂离子快速传输通道的{010}晶面的暴露，{010}晶面的面积占比>20％，为离子快速迁移提供更多通道，提高电极反应动力学。
需要说明的是，本发明技术方案与传统的金属离子掺杂的LLO材料相比，其关键区别在于，本发明是通过多阳离子组分设计形成高熵固溶体，这种组分设计可以提高系统构型熵，诱导具有锂离子快速传输通道的{010}晶面的暴露，从而提高材料的电化学性能；而传统的单金属离子或多金属离子掺杂，则是以较高的金属-氧键能提升晶体结构的稳定性，实现材料电化学性能的提升。
本发明的原理如下：
多组分材料体系中的构型熵(Sconfig)主要依赖于元素的种类及其摩尔分数，可以根据以下公式量化：
式(1)中，xi和xj分别为阳离子和阴离子的摩尔分数，R是气体常数。
材料中不同晶面暴露的表面能一般与温度、体系中的构型熵(Sconfig)和振动熵(Svib)相关，可用公式表示为：
γ(T)＝γ0–(T/A)(Sconfig+Svib)    (2)；
式(2)中，γ0为0K时材料的表面能，A为亥姆霍兹是自由能，T为温度。
由此可以看出，组分简单、熵值低的系统表面能主要受温度的影响，而组分多、熵值高的系统表面能主要受构型熵的影响；本发明通过多阳离子高熵组分调控，实现了特定性{010}晶面的大面积暴露，提高电极材料结构的稳定性和电化学性能。
为实现上述目的，本发明具体提出如下技术方案：
本发明提供了一种富锂层状氧化物材料，所述富锂层状氧化物材料的一次颗粒为{010}晶面暴露的多面体，且{010}晶面的面积占比>20％，优选为30～45％，更优选为35～40％，具体可为36.4％、37.0％、37.2％、37.5％、37.4％或38.3％。
在本发明中，所述富锂层状氧化物材料的构型熵值优选为6.0～9.0，具体可为6.0、6.71、7.45、7.48、7.80、7.89、8.85或9.0。
在本发明中，所述富锂层状氧化物材料的化学通式优选为：Li(LiaNabMncNidCoeMf)O2，其中，M为Mg、B、Al、Ti、Zr、Nb、Mo和W中的一种或多种，0<a≤0.3，0<b≤0.05，0.4<c≤0.7，d＞0，e＞0，f＞0，且a+b+c+d+e+f＝1。
在本发明提供的一个实施例中，所述富锂层状氧化物材料的化学式具体为以下化学式中的任一种：
Li(Li0.18Na0.02Ni0.1552Co0.0776Mn0.5432Al0.008Ti0.016)O2；
Li(Li0.14Na0.01Ni0.20825Co0.12495Mn0.4998Zr0.0170)O2；
Li(Li0.14Na0.01Ni0.206125Co0.123675Mn0.4947Mg0.0085Ti0.017)O2；
Li(Li0.19Na0.01Ni0.20825Co0.20825Mn0.4165Ti0.0085Zr0.0085)O2；
Li(Li0.09Na0.01Ni0.2205Co0.2205Mn0.441Nb0.009Mo0.009)O2；
Li(Li0.18Na0.02Ni0.1568Co0.1568Mn0.4704Zr0.008Ti0.008)O2；
Li(Li0.14Na0.01Ni0.1649Co0.1649Mn0.4947Al0.0085Zr0.017)O2。
本发明还提供了一种上述技术方案所述的富锂层状氧化物材料的制备方法，包括以下步骤：
制备锰镍钴氢氧化物前驱体，将所述锰镍钴氢氧化物前驱体、锂源化合物、钠源化合物和M源化合物混合，在有氧条件下焙烧，得到富锂层状氧化物材料；
所述M源化合物中的M为Mg、B、Al、Ti、Zr、Nb、Mo和W中的一种或多种；
所述富锂层状氧化物材料的一次颗粒为{010}晶面暴露的多面体，且{010}晶面的面积占比>20％。
在本发明提供的制备方法中，所述制备锰镍钴氢氧化物前驱体的具体步骤包括：
a)将锰的可溶性盐、镍的可溶性盐、钴的可溶性盐和水混合，得到混合盐溶液；
b)将所述混合盐溶液、氢氧化钠和络合剂混合，并控制所述氢氧化钠和络合剂的用量使混合体系的pH值维持在10～13进行络合与沉淀反应，得到沉淀物；
c)将所述沉淀物进行洗涤和干燥，得到锰镍钴氢氧化物前驱体。
在本发明提供的上述锰镍钴氢氧化物前驱体制备步骤中，步骤a)中，所述锰的可溶性盐优选为锰的硫酸盐、锰的氯化物和锰的硝酸盐中的一种或多种；所述镍的可溶性盐优选为镍的硫酸盐、镍的氯化物和镍的硝酸盐中的一种或多种；所述钴的可溶性盐优选为钴的硫酸盐、钴的氯化物和钴的硝酸盐中的一种或多种；所述混合盐溶中金属离子的总浓度优选为1～3mol/L，具体可为1mol/L、1.5mol/L、1.8mol/L、2mol/L、2.5mol/L或3mol/L。
在本发明提供的上述锰镍钴氢氧化物前驱体制备步骤中，步骤b)中，所述氢氧化钠优选以氢氧化钠水溶液的形式参与混合，所述氢氧化钠水溶液的浓度优选为0.5～3mol/L，具体可为0.5mol/L、1mol/L、1.5mol/L、2mol/L、2.5mol/L或3mol/L；所述络合剂优选为氨水、乙二胺四乙酸(EDTA)和乙二胺中的一种或多种；所述络合剂以络合剂水溶液的形式参与混合，所述络合剂水溶液的浓度优选为1～10mol/L，具体可为1mol/L、1.5mol/L、2mol/L、2.5mol/L、3mol/L、3.5mol/L、4mol/L、4.5mol/L、5mol/L、5.5mol/L、6mol/L、6.5mol/L、7.5mol/L、8mol/L、8.5mol/L、9mol/L、9.5mol/L或10mol/L；所述混合优选在添加有水作为底液的反应釜中进行。
在本发明提供的上述锰镍钴氢氧化物前驱体制备步骤中，步骤b)中，所述混合体系的pH值具体可维持在10、10.1、10.2、10.3、10.4、10.5、10.6、 10.7、10.8、10.9、11、11.1、11.2、11.3、11.4、11.5、11.6、11.7、11.8、11.9、12、12.1、12.2、12.3、12.4、12.5、12.7、12.8、12.9或13；所述络合与沉淀反应的搅拌速率优选为200～800r/min，具体可为200r/min、250r/min、300r/min、350r/min、400r/min、450r/min、500r/min、550r/min、600r/min、650r/min、700r/min、750r/min或800r/min；所述络合与沉淀反应的温度优选为30～70℃，具体可为30℃、35℃、40℃、45℃、50℃、55℃、56℃、60℃、65℃或70℃；所述络合与沉淀反应的时间优选为10～50h，具体可为10h、15h、20h、25h、30h、35h、40h、42h、45h或50h。
在本发明提供的上述锰镍钴氢氧化物前驱体制备步骤中，步骤c)中，所述干燥的温度优选为100～300℃，具体可为100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃、290℃或300℃。
在本发明提供的制备方法中，所述锂源化合物优选为LiOH、Li2CO3、Li2SO4、LiCl和LiNO3中的一种或多种；所述钠源化合物优选为Na2CO3和/或NaHCO3；所述M源化合物优选为M的氧化物、M的氢氧化物、M的碳酸盐和M的硫酸盐中的一种或多种。
在本发明提供的制备方法中，所述有氧条件优选为空气气氛或纯氧气氛；所述焙烧的方式优选为分步焙烧，其具体过程包括：
i)从环境温度升温至第一焙烧温度，进行一次保温焙烧；
ii)继续升温至第二焙烧温度，进行二次保温焙烧。
在本发明提供的上述焙烧过程中，步骤i)中，所述第一焙烧温度优选为300～600℃，具体可为300℃、320℃、350℃、370℃、400℃、420℃、450℃、470℃、500℃、520℃、550℃、570℃或600℃；升温至所述第一焙烧温度的升温速率优选为1～5℃/min，具体可为1℃/min、1.5℃/min、2℃/min、2.5℃/min、3℃/min、3.5℃/min、4℃/min、4.5℃/min或5℃/min；所述一次保温焙烧的时间优选为2～8h，具体可为2h、2.5h、3h、3.5h、4h、4.5h、5h、5.5h、6h、6.5h、7h、7.5h或8h。
在本发明提供的上述焙烧过程中，步骤ii)中，所述第二焙烧温度优选为800～1000℃，具体可为800℃、810℃、820℃、830℃、840℃、850℃、860℃、 870℃、880℃、890℃、900℃、910℃、920℃、930℃、940℃、950℃、960℃、970℃、980℃、990℃或1000℃；升温至所述第二焙烧温度的升温速率优选为1～5℃/min，具体可为1℃/min、1.5℃/min、2℃/min、2.5℃/min、3℃/min、3.5℃/min、4℃/min、4.5℃/min或5℃/min；所述二次保温焙烧的时间优选为10～20h，具体可为10h、10.5h、11h、11.5h、12h、12.5h、13h、13.5h、14h、14.5h、15h、15.5h、16h、16.5h、17h、17.5h、18h、18.5h、19h、19.5h或20h；
在本发明提供的上述焙烧过程中，有氧条件优选采用持续向所用焙烧设备中通入含氧气体的方式实现；其中，步骤i)的含氧气体进气速率优选为0.5～5m3/h，具体可为0.5m3/h、1m3/h、1.5m3/h、2m3/h、2.5m3/h、3m3/h、3.5m3/h、4m3/h、4.5m3/h或5m3/h；步骤ii)的含氧气体进气速率优选为0.5～5m3/h，具体可为0.5m3/h、1m3/h、1.5m3/h、2m3/h、2.5m3/h、3m3/h、3.5m3/h、4m3/h、4.5m3/h或5m3/h。
在本发明提供的制备方法中，所述焙烧结束后，优选将得到的产物冷却后进行粉碎和过筛。
本发明还提供了一种锂离子二次电池，包括正极、负极、电解液和介于正极与负极之间的隔膜；其中，所述正极的材料包括上述技术方案所述的富锂层状氧化物材料或上述技术方案所述制备方法制得的富锂层状氧化物材料。
本发明还提供了一种用电装置，所述用电装置安装有上述技术方案所述的锂离子二次电池。
为更清楚起见，下面通过以下实施例和对比例进行详细说明。
实施例1
按照摩尔比Ni/Co/Mn＝20:10:70的比例称取硫酸镍、硫酸钴、硫酸锰，并溶解于去离子水中配制成2mol/L的混合盐溶液A；配制浓度为2mol/L的NaOH溶液B和浓度为2mol/L的氨水络合剂溶液C；在反应釜中加入去离子水作为底液，将溶液A、B、C同时泵入反应釜中进行络合与沉淀反应，控制NaOH溶液和氨水络合剂溶液的流速，使反应釜中混合反应液的pH始终保持在11.5±0.05的范围内，反应釜内混合溶液搅拌速度设置为400r/min，反应温度为55℃，持续反应36h后，将得到的沉淀物排出，去离子水洗涤并烘干，烘干温度为150℃，得到锰镍钴氢氧化物前驱体P。
称取1000g的锰镍钴氢氧化物前驱体P、610g的碳酸锂、29.4g的碳酸钠、11.3g的三氧化二铝和17.8g的二氧化钛，采用高混机进行充分混合，得到混合物Q。
将上述混合物Q放置于空气气氛炉中进行两步焙烧，具体过程为：首先按照3℃/min的升温速率将炉温从室温升至550℃，在此温度下焙烧4h，升温和保温焙烧的过程中持续向炉内通入空气，进气速率为2.5m3/h；然后按照3℃/min的升温速率将炉温继续升温至900℃，在此温度下焙烧12h，升温和保温焙烧的过程中持续向炉内通入空气，进气速率为2.5m3/h。
焙烧结束后，随炉冷却，然后将产物进行粉碎，过筛，得到富锂层状氧化物材料Li(Li0.18Na0.02Ni0.1552Co0.0776Mn0.5432Al0.008Ti0.016)O2。
对本实施例制备的富锂层状氧化物材料进行X射线衍射(XRD)表征，结果如图1所示，图1为本发明提供的实施例1富锂层状氧化物材料的XRD图。通过图1可以看出，该材料除了20°～25°之间属于C2/m空间点群的单斜结构的较弱衍射峰以外，其余衍射峰可对应于六方层状结构，说明多组分设计未改变材料的体相结构特征。
对本实施例制备的富锂层状氧化物材料进行高分辨率的透射电镜(HRTEM)表征，并绘制快速傅里叶变换图谱，结果如图2所示，图2为本发明提供的实施例1富锂层状氧化物材料的HRTEM图及其快速傅里叶变换图，其中，左图为HRTEM图，右图为快速傅里叶变换图谱。通过图2可以看出，该材料的晶面间距为0.47nm，与六方相(003)晶面以及单斜结构富锂组分的(001)晶面相匹配；快速傅立叶变换图证明，该材料的顶部暴露晶面为(003)晶面。
对本实施例制备的富锂层状氧化物材料进行扫描电镜(SEM)观察，并绘制其一次颗粒的结构示意图，结果如图3所示，图3为本发明提供的实施例1富锂层状氧化物材料的SEM图与一次颗粒结构示意图，其中，左图为SEM图，右图为一次颗粒的结构示意图。通过图3中的左图可以看出，该材料由直径约1μm的多面体团聚而成；根据图3中的右图可以看出，该材料一次颗粒的顶部暴露晶面为{001}晶面，侧面为{010}晶面，{010}晶面的原子排列呈开放结构，有利于锂离子的输运。
实施例2
按照摩尔比Ni/Co/Mn＝25:15:60的比例称取氯化镍、氯化钴、氯化锰，并溶解于去离子水中配制成1.8mol/L的混合盐溶液A；配制浓度为1.8mol/L的NaOH溶液B和浓度为2.5mol/L的氨水络合剂溶液C；在反应釜中加入去离子水作为底液，将溶液A、B、C同时泵入反应釜中进行络合与沉淀反应，控制NaOH溶液和氨水络合剂溶液的流速，使反应釜中混合反应液的pH始终保持在11.8±0.05的范围内，反应釜内混合溶液搅拌速度设置为600r/min，反应温度为50℃，持续反应36h后，将得到的沉淀物排出，去离子水洗涤并烘干，烘干温度为160℃，得到锰镍钴氢氧化物前驱体P。
称取1000g的锰镍钴氢氧化物前驱体P、550g的碳酸锂、13.9g的碳酸钠和27.1g的二氧化锆，采用高混机进行充分混合，得到混合物Q。
将上述混合物Q放置于氧气气氛炉中进行两步焙烧，具体过程为：首先按照2.5℃/min的升温速率将炉温从室温升至500℃，在此温度下焙烧6h，升温和保温焙烧的过程中持续向炉内通入氧气，进气速率为3m3/h；然后按照2.5℃/min的升温速率将炉温继续升温至880℃，在此温度下焙烧10h，升温和保温焙烧的过程中持续向炉内通入氧气，进气速率为3m3/h。
焙烧结束后，随炉冷却，然后将产物进行粉碎，过筛，得到富锂层状氧化物材料Li(Li0.14Na0.01Ni0.20825Co0.12495Mn0.4998Zr0.0170)O2。
实施例3
按照摩尔比Ni/Co/Mn＝25:15:60的比例称取氯化镍、氯化钴、氯化锰，并溶解于去离子水中配制成2.5mol/L的混合盐溶液A；配制浓度为2mol/L的NaOH溶液B和浓度为3mol/L的乙二胺络合剂溶液C；在反应釜中加入去离子水作为底液，将溶液A、B、C同时泵入反应釜中进行络合与沉淀反应，控制NaOH溶液和乙二胺络合剂溶液的流速，使反应釜中混合反应液的pH始终保持在11.6±0.05的范围内，反应釜内混合溶液搅拌速度设置为500r/min，反应温度为60℃，持续反应40h后，将得到的沉淀物排出，去离子水洗涤并烘干，烘干温度为180℃，得到锰镍钴氢氧化物前驱体P。
称取1000g的锰镍钴氢氧化物前驱体P、820g的硫酸锂、11.0g的碳酸氢钠、9.3g的碳酸镁和27.1g的二氧化钛，采用高混机进行充分混合，得到混合 物Q。
将上述混合物Q放置于氧气气氛炉中进行两步焙烧，具体过程为：首先按照4℃/min的升温速率将炉温从室温升至550℃，在此温度下焙烧5h，升温和保温焙烧的过程中持续向炉内通入氧气，进气速率为5m3/h；然后按照4℃/min的升温速率将炉温继续升温至920℃，在此温度下焙烧12h，升温和保温焙烧的过程中持续向炉内通入氧气，进气速率为5m3/h。
焙烧结束后，随炉冷却，然后将产物进行粉碎，过筛，得到富锂层状氧化物材料Li(Li0.14Na0.01Ni0.206125Co0.123675Mn0.4947Mg0.0085Ti0.017)O2。
实施例4
按照摩尔比Ni/Co/Mn＝25:25:50的比例称取硫酸镍、氯化钴、硫酸锰，并溶解于去离子水中配制成3mol/L的混合盐溶液A；配制浓度为2.5mol/L的NaOH溶液B和浓度为2mol/L的EDTA络合剂溶液C；在反应釜中加入去离子水作为底液，将溶液A、B、C同时泵入反应釜中进行络合与沉淀反应，控制NaOH溶液和EDTA络合剂溶液的流速，使反应釜中混合反应液的pH始终保持在12.0±0.05的范围内，反应釜内混合溶液搅拌速度设置为600r/min，反应温度为65℃，持续反应45h后，将得到的沉淀物排出，去离子水洗涤并烘干，烘干温度为160℃，得到锰镍钴氢氧化物前驱体P。
称取1000g的锰镍钴氢氧化物前驱体P、580g的碳酸锂、11.0g的碳酸氢钠、8.9g的二氧化钛和13.5g的二氧化锆，采用高混机进行充分混合，得到混合物Q。
将上述混合物Q放置于空气气氛炉中进行两步焙烧，具体过程为：首先按照2℃/min的升温速率将炉温从室温升至600℃，在此温度下焙烧4h，升温和保温焙烧的过程中持续向炉内通入空气，进气速率为3m3/h；然后按照2℃/min的升温速率将炉温继续升温至950℃，在此温度下焙烧10h，升温和保温焙烧的过程中持续向炉内通入空气，进气速率为3m3/h。
焙烧结束后，随炉冷却，然后将产物进行粉碎，过筛，得到富锂层状氧化物材料Li(Li0.19Na0.01Ni0.20825Co0.20825Mn0.4165Ti0.0085Zr0.0085)O2。
实施例5
按照摩尔比Ni/Co/Mn＝25:25:50的比例称取氯化镍、硫酸钴、氯化锰， 并溶解于去离子水中配制成1.5mol/L的混合盐溶液A；配制浓度为1mol/L的NaOH溶液B和浓度为2mol/L的氨水络合剂溶液C；在反应釜中加入去离子水作为底液，将溶液A、B、C同时泵入反应釜中进行络合与沉淀反应，控制NaOH溶液和氨水络合剂溶液的流速，使反应釜中混合反应液的pH始终保持在12.5±0.05的范围内，反应釜内混合溶液搅拌速度设置为800r/min，反应温度为60℃，持续反应40h后，将得到的沉淀物排出，去离子水洗涤并烘干，烘干温度为150℃，得到锰镍钴氢氧化物前驱体P。
称取1000g的锰镍钴氢氧化物前驱体P、570g的氢氧化锂、10.4g的碳酸氢钠、29.5g的五氧化二铌和16.2g的三氧化钼，采用高混机进行充分混合，得到混合物Q。
将上述混合物Q放置于氧气气氛炉中进行两步焙烧，具体过程为：首先按照4℃/min的升温速率将炉温从室温升至600℃，在此温度下焙烧3h，升温和保温焙烧的过程中持续向炉内通入氧气，进气速率为2m3/h；然后按照4℃/min的升温速率将炉温继续升温至980℃，在此温度下焙烧15h，升温和保温焙烧的过程中持续向炉内通入氧气，进气速率为2m3/h。
焙烧结束后，随炉冷却，然后将产物进行粉碎，过筛，得到富锂层状氧化物材料Li(Li0.09Na0.01Ni0.2205Co0.2205Mn0.441Nb0.009Mo0.009)O2。
实施例6
按照摩尔比Ni/Co/Mn＝20:20:60的比例称取氯化镍、硫酸钴、氯化锰，并溶解于去离子水中配制成2.5mol/L的混合盐溶液A；配制浓度为1.5mol/L的NaOH溶液B和浓度为5mol/L的乙二胺络合剂溶液C；在反应釜中加入去离子水作为底液，将溶液A、B、C同时泵入反应釜中进行络合与沉淀反应，控制NaOH溶液和乙二胺络合剂溶液的流速，使反应釜中混合反应液的pH始终保持在11.3±0.05的范围内，反应釜内混合溶液搅拌速度设置为600r/min，反应温度为55℃，持续反应50h后，将得到的沉淀物排出，去离子水洗涤并烘干，烘干温度为160℃，得到锰镍钴氢氧化物前驱体P。
称取1000g的锰镍钴氢氧化物前驱体P、670g的氢氧化锂、29.4g的碳酸钠、13.5g的二氧化锆和8.9g的二氧化钛，采用高混机进行充分混合，得到混合物Q。
将上述混合物Q放置于空气气氛炉中进行两步焙烧，具体过程为：首先按照3℃/min的升温速率将炉温从室温升至550℃，在此温度下焙烧6h，升温和保温焙烧的过程中持续向炉内通入空气，进气速率为3m3/h；然后按照3℃/min的升温速率将炉温继续升温至960℃，在此温度下焙烧12h，升温和保温焙烧的过程中持续向炉内通入空气，进气速率为3m3/h。
焙烧结束后，随炉冷却，然后将产物进行粉碎，过筛，得到富锂层状氧化物材料Li(Li0.18Na0.02Ni0.1568Co0.1568Mn0.4704Zr0.008Ti0.008)O2。
实施例7
按照摩尔比Ni/Co/Mn＝20:20:60的比例称取氯化镍、硫酸钴、氯化锰，并溶解于去离子水中配制成1.8mol/L的混合盐溶液A；配制浓度为2.5mol/L的NaOH溶液B和浓度为1mol/L的EDTA络合剂溶液C；在反应釜中加入去离子水作为底液，将溶液A、B、C同时泵入反应釜中进行络合与沉淀反应，控制NaOH溶液和EDTA络合剂溶液的流速，使反应釜中混合反应液的pH始终保持在12.8±0.05的范围内，反应釜内混合溶液搅拌速度设置为750r/min，反应温度为56℃，持续反应42h后，将得到的沉淀物排出，去离子水洗涤并烘干，烘干温度为160℃，得到锰镍钴氢氧化物前驱体P。
称取1000g的锰镍钴氢氧化物前驱体P、555g的碳酸锂、13.9g的碳酸钠、11.3g的三氧化二铝和27.1g的二氧化锆，采用高混机进行充分混合，得到混合物Q。
将上述混合物Q放置于氧气气氛炉中进行两步焙烧，具体过程为：首先按照3℃/min的升温速率将炉温从室温升至580℃，在此温度下焙烧6h，升温和保温焙烧的过程中持续向炉内通入氧气，进气速率为5m3/h；然后按照3℃/min的升温速率将炉温继续升温至920℃，在此温度下焙烧18h，升温和保温焙烧的过程中持续向炉内通入氧气，进气速率为5m3/h。
焙烧结束后，随炉冷却，然后将产物进行粉碎，过筛，得到富锂层状氧化物材料Li(Li0.14Na0.01Ni0.1649Co0.1649Mn0.4947Al0.0085Zr0.017)O2。
对比例1
按照摩尔比Ni/Co/Mn＝20:10:70的比例称取硫酸镍、硫酸钴、硫酸锰，并溶解于去离子水中配制成2mol/L的混合盐溶液A；配制浓度为2mol/L的 NaOH溶液B和浓度为2mol/L的氨水络合剂溶液C；在反应釜中加入去离子水作为底液，将溶液A、B、C同时泵入反应釜中进行络合与沉淀反应，控制NaOH碱溶液和氨水络合剂溶液的流速，使反应釜中混合反应液的pH始终保持在11.5±0.05的范围内，反应釜内混合溶液搅拌速度设置为400r/min，反应温度为55℃，持续反应36h后，将得到的沉淀物排出，去离子水洗涤并烘干，烘干温度为150℃，得到锰镍钴氢氧化物前驱体P。
称取1000g的锰镍钴氢氧化物前驱体P和620g的碳酸锂，采用高混机进行充分混合，得到混合物Q。
将上述混合物Q放置于空气气氛炉中进行两步煅烧，具体过程为：首先按照3℃/min的升温速率将炉温从室温升至550℃，在此温度下焙烧4h，升温和保温焙烧的过程中持续向炉内通入空气，进气速率为2.5m3/h；然后按照3℃/min的升温速率将炉温继续升温至900℃，在此温度下焙烧12h，升温和保温焙烧的过程中持续向炉内通入空气，进气速率为2.5m3/h。
焙烧结束后，随炉冷却，然后将产物进行粉碎，过筛，得到富锂层状氧化物材料Li(Li0.2Ni0.16Co0.08Mn0.56)O2。
对比例2
称取620g的碳酸锂、55.8g的四氧化三锰、195.6g的氢氧化镍、98.9g的氢氧化钴、29.4g的碳酸钠、11.3g的三氧化二铝和17.8g的二氧化钛，将上述原材料加入至1000mL去离子水中，搅拌混合均匀，得到混合物A。
将混合物A通过蠕动泵泵入喷雾干燥设备，入液速率设置为0.8L/min，喷雾干燥进风温度设置为250℃，出风温度设置为120℃，载气速率设置为50L/min，高温下混合物中液体蒸发得到金属离子均匀混合的粉末B。
将上述粉末B放置于空气气氛炉中进行两步焙烧，具体过程为：首先按照3℃/min的升温速率将炉温从室温升至550℃，在此温度下焙烧4h，升温和保温焙烧的过程中持续向炉内通入空气，进气速率为2.5m3/h；然后按照3℃/min的升温速率将炉温继续升温至900℃，在此温度下焙烧12h，升温和保温焙烧的过程中持续向炉内通入空气，进气速率为2.5m3/h。
焙烧结束后，随炉冷却，然后将产物进行粉碎，过筛，得到富锂层状氧化物材料Li(Li0.18Na0.02Ni0.1552Co0.0776Mn0.5432Al0.008Ti0.016)O2。
性能效果评价
通过公式(1)计算实施例1～7和对比例1～2所制备的氧化物材料的构型熵，并通过SEM图计算上述材料中{010}晶面的暴露面积占比。结果如表1所示：
表1
在扣式锂二次电池中测试实施例1～7和对比例1～2所制备的氧化物材料作为锂二次电池正极材料时的电化学性能，锂二次电池及其正极极片的具体制作方式为：将所制备的正极材料粉末与乙炔黑、聚偏氟乙烯按照90:5:5的质量比混合，加入适量的N-甲基吡咯烷酮作为分散剂，研磨成浆料；随后将浆料均匀涂覆在铝箔上，120℃真空干燥10h，用对辊机将干燥好的极片进行辊压，使用切片机对铝箔进行裁剪，裁成直径为1.3cm的圆形极片，活性材料的负载量控制在10mg/cm2左右；在氩气气氛手套箱中组装半电池，水分压≤0.1ppm，氧分压≤0.1ppm；以金属锂为对电极，以1M LiPF6(FEC/EC/DMC，体积比为1:1:1)溶液为电解液，组装规格为CR2032型扣式电池，使用恒流充放电模式在室温条件下进行充放电，电压范围为2.0～4.65V，电流密度为50mA/g(0.2C倍率)进行充放电循环100圈；通过电化学阻抗EIS测试对比不同材料的锂离子扩散系数，测试的频率范围为100kHz～0.01Hz；电池倍率性能测试电流密度为50mA/g、 500mA/g、1250mA/g、2500mA/g，分别对应0.2C、2C、5C、10C。
实施例1与对比例1～2所制备的氧化物材料在锂二次电池测试中的循环性能测试结果如图4所示，图4为本发明提供的实施例1、对比例1与对比例2所制备的氧化物材料在锂二次电池测试中的循环性能对比图；实施例1～7与对比例1～2所制备的氧化物材料在锂二次电池测试中的首周充电比容量、首周放电比容量、首周库伦效率，100周后容量保持率以及锂离子扩散系数数据如表2所示：
表2
实施例1与对比例1～2所制备的氧化物材料在锂二次电池测试中的倍率性能测试结果如图5所示，图5为本发明提供的实施例1、对比例1与对比例2所制备的氧化物材料在锂二次电池测试中的倍率性能对比图；实施例1～7与对比例1～2所制备的氧化物材料在锂二次电池测试中的倍率性能数据如表3所示：
表3

通过对比分析表1～3以及图4～5可以看出：1)实施例1～7与对比例1所制备的氧化物材料的构型熵值与{010}晶面的暴露比例呈正相关；2)对比例2虽然引入了多种阳离子的高熵组分设计，构型熵与实施例1相同，但由于采用的喷雾干燥工艺，相较于实施例1的共沉淀反应制备前驱体后混锂煅烧工艺，晶面调控阻力更大，而未能实现{010}晶面的大面积暴露；3)以实施例1～7所制备的氧化物材料作为正极材料的锂二次电池表现出更高的锂离子扩散速率，且循环100周后容量保持率明显高于对比例1～2；4)以实施例1～7所制备的氧化物材料作为正极材料的锂二次电池在10C高倍率下放电容量保持率(10C放电容量/0.2C放电容量)均远高于对比例1～2。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (11)

  1. 一种富锂层状氧化物材料，其特征在于，所述富锂层状氧化物材料的一次颗粒为{010}晶面暴露的多面体，且{010}晶面的面积占比>20％。
  2. 根据权利要求1所述的富锂层状氧化物材料，其特征在于，所述{010}晶面的面积占为30～45％。
  3. 根据权利要求1所述的富锂层状氧化物材料，其特征在于，所述富锂层状氧化物材料的构型熵值为6.0～9.0。
  4. 根据权利要求1～3任一项所述的富锂层状氧化物材料，其特征在于，所述富锂层状氧化物材料的化学式为Li(LiaNabMncNidCoeMf)O2，其中，M为Mg、B、Al、Ti、Zr、Nb、Mo和W中的一种或多种，0<a≤0.3，0<b≤0.05，0.4<c≤0.7，d＞0，e＞0，f＞0，且a+b+c+d+e+f＝1。
  5. 一种富锂层状氧化物材料的制备方法，其特征在于，包括以下步骤：
    制备锰镍钴氢氧化物前驱体，将所述锰镍钴氢氧化物前驱体、锂源化合物、钠源化合物和M源化合物混合，在有氧条件下焙烧，得到富锂层状氧化物材料；
    所述M源化合物中的M为Mg、B、Al、Ti、Zr、Nb、Mo和W中的一种或多种；
    所述富锂层状氧化物材料的一次颗粒为{010}晶面暴露的多面体，且{010}晶面的面积占比>20％。
  6. 根据权利要求5所述的制备方法，其特征在于，所述制备锰镍钴氢氧化物前驱体的具体步骤包括：
    a)将锰的可溶性盐、镍的可溶性盐、钴的可溶性盐和水混合，得到混合盐溶液；
    b)将所述混合盐溶液、氢氧化钠和络合剂混合，并控制所述氢氧化钠和络合剂的用量使混合体系的pH值维持在10～13进行络合与沉淀反应，得到沉淀物；
    c)将所述沉淀物进行洗涤和干燥，得到锰镍钴氢氧化物前驱体。
  7. 根据权利要求6所述的制备方法，其特征在于，所述具体步骤满足以 下条件中的至少一个条件：
    所述锰的可溶性盐为锰的硫酸盐、锰的氯化物和锰的硝酸盐中的一种或多种；
    所述镍的可溶性盐为镍的硫酸盐、镍的氯化物和镍的硝酸盐中的一种或多种；
    所述钴的可溶性盐为钴的硫酸盐、钴的氯化物和钴的硝酸盐中的一种或多种；
    所述络合剂为氨水、乙二胺四乙酸和乙二胺中的一种或多种；
    所述混合盐溶中金属离子的总浓度为1～3mol/L；
    所述氢氧化钠以氢氧化钠水溶液的形式参与混合，所述氢氧化钠水溶液的浓度为0.5～3mol/L；
    所述络合剂以络合剂水溶液的形式参与混合，所述络合剂水溶液的浓度为1～10mol/L；
    所述络合与沉淀反应的搅拌速率为200～800r/min；
    所述络合与沉淀反应的温度为30～70℃；
    所述络合与沉淀反应的时间为10～50h。
  8. 根据权利要求5所述的制备方法，其特征在于，所述锂源化合物为LiOH、Li2CO3、Li2SO4、LiCl和LiNO3中的一种或多种；所述钠源化合物为Na2CO3和/或NaHCO3；所述M源化合物为M的氧化物、M的氢氧化物、M的碳酸盐和M的硫酸盐中的一种或多种。
  9. 根据权利要求5所述的制备方法，其特征在于，所述焙烧的方式为分步焙烧，具体过程包括：
    i)从环境温度升温至第一焙烧温度，进行一次保温焙烧；
    所述第一焙烧温度为300～600℃；升温至所述第一焙烧温度的升温速率为1～5℃/min；所述一次保温焙烧的时间为2～8h；
    ii)继续升温至第二焙烧温度，进行二次保温焙烧；
    所述第二焙烧温度为800～1000℃；升温至所述第二焙烧温度的升温速率为1～5℃/min；所述二次保温焙烧的时间为10～20h；
    焙烧过程中，持续向所用焙烧设备中通入含氧气体，步骤i)的含氧气体 进气速率为0.5～5m3/h，步骤ii)的含氧气体进气速率为0.5～5m3/h。
  10. 一种锂离子二次电池，其特征在于，所述锂离子二次电池的正极材料包括权利要求1～4任一项所述的富锂层状氧化物材料或权利要求5～9任一项所述制备方法制得的富锂层状氧化物材料。
  11. 一种用电装置，其特征在于，所述用电装置安装有权利要求10所述的锂离子二次电池。
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