WO2023226554A1 - 一种高电压镍钴锰酸锂正极材料及其制备方法和应用 - Google Patents

一种高电压镍钴锰酸锂正极材料及其制备方法和应用 Download PDF

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WO2023226554A1
WO2023226554A1 PCT/CN2023/082551 CN2023082551W WO2023226554A1 WO 2023226554 A1 WO2023226554 A1 WO 2023226554A1 CN 2023082551 W CN2023082551 W CN 2023082551W WO 2023226554 A1 WO2023226554 A1 WO 2023226554A1
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nickel cobalt
lithium nickel
cathode material
manganate cathode
cobalt manganate
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PCT/CN2023/082551
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English (en)
French (fr)
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余海军
谢英豪
李爱霞
张学梅
李长东
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2023226554A1 publication Critical patent/WO2023226554A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/253—Halides
    • C01F17/265—Fluorides
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of battery materials, and particularly relates to a high-voltage lithium nickel cobalt manganate cathode material and its preparation method and application.
  • Lithium-ion batteries have the characteristics of high voltage, high specific energy, long life, no memory effect, and small self-discharge. They have been widely used in various portable electronic products and have potential application markets in fields such as hybrid vehicles and pure electric vehicles. .
  • Currently commercially available lithium battery cathode materials mainly include lithium cobalt oxide, lithium manganate, lithium iron phosphate, ternary cathode materials, etc.
  • the ternary cathode material has the advantages of high energy density and good cycle performance, and has gradually replaced the application of lithium iron phosphate in the power and digital fields. As the country's requirements for power battery energy density increase to more than 300Wh/Kg, the research and development progress of high-voltage cathode materials has been greatly promoted.
  • ternary cathode materials used on a large scale on the market include single crystal ternary cathode materials and agglomerated ternary cathode materials.
  • the ternary cathode material undergoes an irreversible phase change under high voltage, which leads to an increase in the interfacial reaction of the electrode/electrolyte, increases the corrosion of the ternary cathode material and the dissolution of transition metal ions, and its layered structure is destroyed, resulting in its capacity Decays quickly and cycle performance decreases. Therefore, the electrochemical performance of existing high-voltage cathode materials under high voltage needs to be further improved.
  • the present invention aims to solve at least one of the technical problems existing in the prior art.
  • the present invention proposes a high-voltage lithium nickel cobalt manganate cathode material and its preparation method and application.
  • the high-voltage lithium nickel cobalt manganate cathode material has good electrochemical properties under high voltage, and its 0.1C discharge The capacity is above 185.7mAh/g, its discharge specific capacity is above 169.7mAh/g after 100 cycles, and the cycle retention rate is above 90.1%.
  • a method for preparing a lithium nickel cobalt manganate cathode material precursor including the following steps:
  • step (3) The mixed liquid obtained in step (2) is subjected to solid-liquid separation to obtain a solid product, which is the precursor of the lithium nickel cobalt manganate cathode material.
  • the lithium nickel cobalt manganate cathode material precursor has the following general chemical formula: Nix Co y Mn z M a (OH) 2+3a ⁇ bMF 3 .
  • the total concentration of metal ions in the mixed salt solution is 0.5-2.0 mol/L.
  • the total concentration of metal ions in the mixed salt solution is 1.0-2.0 mol/L.
  • the concentration of the fluoride salt solution is 0.005-2.0 mol/L.
  • the concentration of the fluorine salt solution is 0.01-1.0 mol/L.
  • the precipitating agent is at least one of sodium hydroxide solution and potassium hydroxide solution.
  • the concentration of the precipitating agent is 1.0-20.0 mol/L.
  • the concentration of the precipitating agent is 4.0-10.0 mol/L.
  • the complexing agent is ammonia water.
  • the concentration of ammonia water is 1.0-15.0 mol/L.
  • the concentration of ammonia water is 6.0-12.0 mol/L.
  • the alkaline bottom liquid is a mixed liquid of sodium hydroxide and ammonia water
  • the pH value of the alkaline bottom liquid is 10.8-11.5
  • the ammonia water concentration is 2.0-10.0g/L.
  • the mixing method of step (2) is to add the fluorine salt solution, the precipitant, the complexing agent and the mixed salt solution obtained in step (1) to the alkaline bottom liquid in parallel flow.
  • the ratio of the amount of M ions added to the amount of fluoride ions is controlled to be (a+b): 3b, and the pH of the mixed solution is controlled to be 10.8-11.5, and the ammonia concentration is 2.0-10.0g/L.
  • the reaction temperature of the reaction in step (2) is 45-65°C.
  • step (2) when the D50 of the material in the mixed liquid is detected to reach 2.0-11.0 ⁇ m, the feeding is stopped.
  • the solid product described in step (3) is also washed, dried, screened and demagnetized.
  • a method for preparing the lithium nickel cobalt manganate cathode material precursor as described above includes the following steps:
  • the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 10.8-11.5 and ammonia water concentration of 2.0-10.0g/L) until it covers the bottom stirring paddle and start stirring;
  • a lithium nickel cobalt manganate cathode material precursor is prepared by the above preparation method.
  • the phase of the lithium nickel cobalt manganate cathode material precursor is spherical or spherical-like.
  • the phase of the lithium nickel cobalt manganate cathode material precursor is secondary particles formed by agglomeration of primary particles, and the particle size of the secondary particles is 2.0-11.0 ⁇ m.
  • crystal grains with a particle size of 10-200 nm are distributed inside and on the surface of the secondary particles.
  • the crystal grains are MF 3 .
  • a lithium nickel cobalt manganate cathode material is prepared from raw materials including the lithium nickel cobalt manganate cathode material precursor as described above.
  • the morphology of the lithium nickel cobalt manganate cathode material is single crystal particles with a particle size of 2.0-8.0 ⁇ m.
  • a method for preparing the lithium nickel cobalt manganate cathode material as described above including the following steps: mixing the lithium nickel cobalt manganate cathode material precursor and a lithium source, sintering it once in an oxygen atmosphere, and then sintering it twice. After sintering, cooling and crushing, the lithium ion battery cathode material is obtained.
  • the mixing operation is to mix the lithium nickel cobalt manganate cathode material precursor and the lithium source according to a molar ratio of nickel cobalt manganese element to lithium element of 1: (1.0-1.2).
  • the lithium source is at least one of lithium carbonate, lithium nitrate and lithium oxalate.
  • the primary sintering is to mix the lithium nickel cobalt manganate cathode material precursor and the lithium source, and then heat it up in an oxygen atmosphere.
  • the temperature rise rate is 0.5-10°C/min, and the temperature rise gradient is from room temperature. Raise the temperature to 300-600°C and keep warm for 1-2 hours.
  • the secondary sintering is to continue to raise the temperature to 1050-1200°C and keep the temperature for 12-36 hours after the primary sintering is completed.
  • a method for preparing the lithium nickel cobalt manganate cathode material as described above includes the following steps:
  • the heating rate is 0.5-10°C/min
  • the heating gradient is from room temperature to 300-600°C, holding for 1-2h, continuing to heat to 1050-1200°C, holding for 12-36h, and then crushed
  • the high-voltage lithium nickel cobalt manganate cathode material is obtained.
  • An electrode includes the lithium nickel cobalt manganate cathode material as described above.
  • a battery includes the electrode as described above.
  • the lithium nickel cobalt manganate cathode material of the present invention is prepared by first preparing a high-voltage lithium nickel cobalt manganate cathode material precursor through a co-precipitation method, and then mixing and sintering it with a lithium source. Since the lithium nickel cobalt manganate cathode material is doped with lanthanide metal elements and coated with lanthanide metal fluoride, the cycle stability of the material under high voltage can be further improved.
  • lanthanide metal ions react with hydroxide to form hydroxide, and at the same time react with nickel cobalt manganese hydroxide to form co-precipitation, obtaining a nickel cobalt manganese hydroxide precursor doped with lanthanide metal elements, doped with lanthanum Lanthanide metal elements can further improve the lattice stability, thereby further improving the cycle performance of subsequent cathode materials; on the other hand, lanthanide metal ions react with fluoride ions to form lanthanide metal fluoride precipitates, which are in the form of small grains and The nickel-cobalt-manganese hydroxide precursor is mixed and adheres to the interior and surface of the precursor.
  • the cathode material When the cathode material is subsequently sintered at high temperature, it can be further melted to form a surface coating layer, which solves the problem that the coating agent needs to be processed during sintering of the cathode material.
  • the problem of adding mixed materials first and then sintering, coating can further improve the cycle performance of the material.
  • Lanthanide metal fluorides are easily hydrolyzed at high temperatures. First, they are vacuum dried at 100-150°C for 2-3h to remove surface water. Secondly, they are kept at 300-600°C for 1-2h to remove the crystallization water of the material. Finally, they are dried at 1050-1200°C. The fluoride melts at °C , and kept for 12-36 hours, and then sintered to prepare lithium nickel cobalt manganate cathode material.
  • Figure 1 is an SEM image of the lithium nickel cobalt manganate cathode material precursor in Example 1 of the present invention
  • Figure 2 is an SEM image of the lithium nickel cobalt manganate cathode material in Example 1 of the present invention
  • Figure 3 is an SEM image of the lithium nickel cobalt manganate cathode material precursor of Comparative Example 1 of the present invention.
  • a method for preparing a high-voltage lithium nickel cobalt manganate cathode material precursor including the following steps:
  • the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 11.3 and an ammonia concentration of 8.0g/L) until it covers the bottom stirring paddle and start stirring;
  • a high-voltage lithium nickel cobalt manganate cathode material precursor is prepared by the above preparation method. Its SEM picture is shown in Figure 1, and its chemical formula is Ni 0.65 Co 0.1 Mn 0.25 Ho 0.008 (OH) 2.024 ⁇ 0.008HoF 3 , its morphology is spherical or quasi-spherical, secondary particles formed by agglomeration of primary particles, the size of the secondary particles is 4.0 ⁇ m; there are small crystal grains distributed inside and on the surface of the spherical particles, the size of the small crystal grains is 10nm- 200nm.
  • a high-voltage lithium nickel cobalt manganate cathode material is prepared by sintering the above precursor and lithium source. Its SEM image is shown in Figure 2. Its general chemical formula is LiNi 0.65 Co 0.1 Mn 0.25 Ho 0.008 O 2.012 ⁇ 0.008 MF 3 has a morphology of single crystal particles and a particle size of 6.0 ⁇ m.
  • a method for preparing high-voltage lithium nickel cobalt manganate cathode material including the following steps:
  • the molar ratio of nickel, cobalt, manganese and lithium elements being 1:1.2, mix the above precursor with lithium nitrate and then heat it up in an oxygen atmosphere.
  • the heating rate is 10°C/min, and the heating gradient is from room temperature to 600°C and maintained for 1 hour. , continue to raise the temperature to 1150°C and keep it for 32 hours, and then crush, screen, and remove iron to obtain the high-voltage lithium nickel cobalt manganate cathode material.
  • a method for preparing a high-voltage lithium nickel cobalt manganate cathode material precursor including the following steps:
  • the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 11.1 and an ammonia concentration of 6.0g/L) until it covers the bottom stirring paddle and start stirring;
  • a high-voltage lithium nickel cobalt manganate cathode material precursor which is prepared by the above preparation method. Its chemical formula is Ni 0.6 Co 0.2 Mn 0.2 Tm 0.005 (OH) 2.015 ⁇ 0.005TmF 3 , and its morphology is spherical or quasi-spherical. , secondary particles formed by agglomeration of primary particles, the size of the secondary particles is 7.0 ⁇ m; there are small crystal grains distributed inside and on the surface of the spherical particles, and the size of the small crystal grains is 10nm-200nm.
  • a high-voltage lithium nickel cobalt manganate cathode material is prepared by sintering the above-mentioned precursor and lithium source. Its general chemical formula is LiNi 0.6 Co 0.2 Mn 0.2 Tm 0.005 O 2.0075 ⁇ 0.005MF 3 , and its morphology is single crystal. Particles, the particle size is 2.0 ⁇ m.
  • a method for preparing high-voltage lithium nickel cobalt manganate cathode material including the following steps:
  • the molar ratio of nickel, cobalt, manganese and lithium elements being 1:1.1, mix the above precursor with lithium carbonate and then heat it up in an air atmosphere.
  • the heating rate is 0.5°C/min, and the heating gradient is from room temperature to 300°C and maintained for 2 hours. , continue to heat up to 1200°C and keep it for 12 hours, and then crush, screen, and remove iron to obtain the high-voltage lithium nickel cobalt manganate cathode material.
  • a method for preparing a high-voltage lithium nickel cobalt manganate cathode material precursor including the following steps:
  • the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 10.8 and an ammonia concentration of 2.0g/L) until it covers the bottom stirring paddle and start stirring;
  • a high-voltage lithium nickel cobalt manganate cathode material precursor which is prepared by the above preparation method. Its chemical formula is Ni 0.5 Co 0.2 Mn 0.3 Yb 0.004 (OH) 2.012 ⁇ 0.008YbF 3 , and its morphology is spherical or quasi-spherical. , secondary particles formed by agglomeration of primary particles, the size of the secondary particles is 11.0 ⁇ m; there are small crystal grains distributed inside and on the surface of the spherical particles, and the size of the small crystal grains is 10nm-200nm.
  • a high-voltage lithium nickel cobalt manganate cathode material is prepared by sintering the above precursor and a lithium source. Its general chemical formula is LiNi 0.5 Co 0.2 Mn 0.3 Yb 0.004 O 2.006 ⁇ 0.008YbF 3 , and its morphology is single crystal. Particles, the particle size is 8 ⁇ m.
  • a method for preparing high-voltage lithium nickel cobalt manganate cathode material including the following steps:
  • the molar ratio of nickel, cobalt, manganese and lithium elements being 1:1.0, mix the above precursor and lithium oxalate and then heat it up in an air atmosphere.
  • the heating rate is 5°C/min, and the heating gradient is from room temperature to 450°C and holding for 1.5 h, continue to raise the temperature to 1100°C and keep it for 36 hours, and then crush, screen, and remove iron to obtain the high-voltage lithium nickel cobalt manganate cathode material.
  • a method for preparing a lithium nickel cobalt manganate cathode material precursor including the following steps:
  • the bottom liquid is a mixture of sodium hydroxide and ammonia water, its pH value is 11.3, and the ammonia concentration The concentration is 8.0g/L) until it covers the bottom stirring paddle and start stirring;
  • the lithium nickel cobalt manganate cathode material precursor is obtained.
  • a lithium nickel cobalt manganate cathode material precursor is prepared by the above preparation method. Its SEM picture is shown in Figure 3. Its chemical formula is Ni 0.65 Co 0.1 Mn 0.25 (OH) 2 and its morphology is spherical or similar. Spherical, secondary particles formed by agglomeration of primary particles. The particle size of the secondary particles is 4.0 ⁇ m.
  • a lithium nickel cobalt manganate cathode material prepared by sintering the above precursor and a lithium source. Its general chemical formula is LiNi 0.65 Co 0.1 Mn 0.25 O 2 . Its morphology is single crystal particles and the particle size is 6.0 ⁇ m. .
  • a method for preparing lithium nickel cobalt manganate cathode material including the following steps:
  • the molar ratio of nickel, cobalt, manganese and lithium elements being 1:1.2, mix the above precursor with lithium nitrate and then heat it up in an oxygen atmosphere.
  • the heating rate is 10°C/min, and the heating gradient is from room temperature to 600°C and maintained for 1 hour. , continue to raise the temperature to 1150°C and keep it for 32 hours, and then crush, screen, and remove iron to obtain the lithium nickel cobalt manganate cathode material.
  • a method for preparing a lithium nickel cobalt manganate cathode material precursor including the following steps:
  • the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 11.1 and an ammonia concentration of 6.0g/L) until it covers the bottom stirring paddle and start stirring;
  • the lithium nickel cobalt manganate cathode material precursor is obtained.
  • a lithium nickel cobalt manganate cathode material precursor which is prepared by the above preparation method. Its chemical formula is Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 . Its morphology is spherical or quasi-spherical, and is formed by agglomeration of primary particles. Secondary particles, secondary The particle size of the particles is 7.0 ⁇ m.
  • a lithium nickel cobalt manganate cathode material prepared by sintering the above-mentioned precursor and a lithium source. Its general chemical formula is LiNi 0.6 Co 0.2 Mn 0.2 O 2 . Its morphology is single crystal particles and the particle size is 2.0 ⁇ m. .
  • a method for preparing lithium nickel cobalt manganate cathode material including the following steps:
  • a method for preparing a lithium nickel cobalt manganate cathode material precursor including the following steps:
  • the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 10.8 and an ammonia concentration of 2.0g/L) until it covers the bottom stirring paddle and start stirring;
  • the lithium nickel cobalt manganate cathode material precursor is obtained.
  • a lithium nickel cobalt manganate cathode material precursor which is prepared by the above preparation method. Its chemical formula is Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 . Its morphology is spherical or quasi-spherical, and is formed by agglomeration of primary particles. Secondary particles, the particle size of the secondary particles is 11.0 ⁇ m.
  • a lithium nickel cobalt manganate cathode material is prepared by sintering the above precursor and a lithium source. Its general chemical formula is LiNi 0.5 Co 0.2 Mn 0.3 O 2 . Its morphology is single crystal particles and the particle size is 8 ⁇ m.
  • a method for preparing lithium nickel cobalt manganate cathode material including the following steps:
  • the molar ratio of nickel, cobalt, manganese and lithium elements being 1:1.0, mix the above precursor and lithium oxalate and then heat it up in an air atmosphere.
  • the heating rate is 5°C/min, and the heating gradient is from room temperature to 450°C and holding for 1.5 h, continue to raise the temperature to 1100°C and keep it for 36 hours, and then crush, sieve, and remove iron to obtain the lithium nickel cobalt manganate cathode material.
  • the cathode materials of Examples 1-3 and Comparative Examples 1-3 were formed into button batteries for electrochemical performance testing of lithium ion batteries.
  • the specific steps were: using N-methylpyrrolidone as the solvent, according to the mass ratio of 9.2:0.5: Mix the cathode material with acetylene black and PVDF at a ratio of 0.3 evenly, apply it on aluminum foil, air dry at 80°C for 8 hours, and then vacuum dry at 120°C for 12 hours. Assemble the battery in an argon-protected glove box.
  • the cathode is a lithium metal sheet
  • the separator is a polypropylene film
  • the electrolyte is 1M LiPF 6 -EC/DMC (1:1, v/v)
  • a 2032 button battery case is used. Assemble the coin cells in an argon-protected glove box, and then conduct electrochemical performance tests at 3.0-4.5V at 25°C.
  • the high-voltage lithium nickel cobalt manganate cathode material of the present invention has good discharge capacity and cycle stability under high voltage. Its 0.1C discharge capacity is above 185.7mAh/g, and it discharges after 100 cycles. The specific capacity is above 169.7mAh/g, and the cycle retention rate is above 90.1%.
  • Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Example 3 with Comparative Example 3, it can be seen that in the preparation of nickel cobalt manganese When no lanthanide metal elements are added in the process of lithium acid phosphate cathode material precursor, the 0.1C discharge capacity under high pressure, discharge specific capacity after 100 cycles and cycle retention rate of the finally prepared lithium nickel cobalt manganate cathode material will all decrease. decline.

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  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

本发明公开了一种镍钴锰酸锂正极材料前驱体的制备方法，其特征在于：包括以下步骤：(1)配制含镍、钴、锰及M元素的可溶性的混合盐溶液，所述M元素为Ho、Tm、Yb、Lu中的至少一种；(2)将氟盐溶液、沉淀剂、络合剂及步骤(1)得到的混合盐溶液与碱性底液混合进行反应，得到混合液；(3)将步骤(2)得到的混合液进行固液分离，得到固体产物即为所述镍钴锰酸锂正极材料前驱体。通过该制备方法制备得到的镍钴锰酸锂正极材料前驱体制备得到的高电压镍钴锰酸锂正极材料在高电压下具有较好的电化学性能。

Description

一种高电压镍钴锰酸锂正极材料及其制备方法和应用 技术领域
本发明属于电池材料技术领域，特别涉及一种高电压镍钴锰酸锂正极材料及其制备方法和应用。
背景技术
锂离子电池具有高电压、高比能量、长寿命、无记忆效应、自放电小等特性，已经广泛应用于各种便携式电子产品，并在混合动力汽车和纯电动汽车等领域有潜在的应用市场。当前商用的锂电池正极材料主要有钴酸锂、锰酸锂、磷酸铁锂、三元正极材料等。三元正极材料具有能量密度高和循环性能好等优点，逐步取代磷酸铁锂在动力和数码领域的应用。伴随着国家对动力电池能量密度的要求的提高到300Wh/Kg以上，极大促进了高电压正极材料的研发进度。
为了进一步提高三元正极材料的容量，提高其工作电压是一种有效的方法，目前市场上大规模使用的高电压正极材料包括单晶三元正极材料和团聚态三元正极材料。但三元正极材料在高电压下发生不可逆相变，导致电极/电解液的界面反应的增加，增大三元正极材料的腐蚀和过渡金属离子的溶出，其层状结构被破坏，导致其容量衰减很快，循环性能下降。因此，现有的高电压正极材料在高电压下的电化学性能有待进一步提高。
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提出一种高电压镍钴锰酸锂正极材料及其制备方法和应用，该高电压镍钴锰酸锂正极材料在高电压下具有较好的电化学性能，其0.1C放电容量在185.7mAh/g以上，其100次循环后放电比容量在169.7mAh/g以上，循环保持率在90.1％以上。
本发明的上述技术目的是通过以下技术方案得以实现的：
一种镍钴锰酸锂正极材料前驱体的制备方法，包括以下步骤：
(1)配制含镍、钴、锰及M元素的可溶性的混合盐溶液，所述M元素为Ho、Tm、Yb、Lu中的至少一种；
(2)将氟盐溶液、沉淀剂、络合剂及步骤(1)得到的混合盐溶液与碱性底液混合进行反应，得到混合液；
(3)将步骤(2)得到的混合液进行固液分离，得到固体产物即为所述镍钴锰酸锂正极材料前驱体。
优选的，所述镍钴锰酸锂正极材料前驱体具有如下化学通式：NixCoyMnzMa(OH)2+3a·bMF3。
优选的，所述混合盐溶液中金属离子总浓度为0.5-2.0mol/L。
进一步优选的，所述混合盐溶液中金属离子总浓度为1.0-2.0mol/L。
优选的，所述氟盐溶液的浓度为0.005-2.0mol/L。
进一步优选的，所述氟盐溶液的浓度为0.01-1.0mol/L。
优选的，所述沉淀剂为氢氧化钠溶液及氢氧化钾溶液中的至少一种。
优选的，所述沉淀剂的浓度为1.0-20.0mol/L。
进一步优选的，所述沉淀剂的浓度为4.0-10.0mol/L。
优选的，所述络合剂为氨水。
优选的，所述氨水的浓度为1.0-15.0mol/L。
进一步优选的，所述氨水的浓度为6.0-12.0mol/L。
优选的，所述碱性底液为氢氧化钠和氨水的混合液，所述碱性底液的pH值为10.8-11.5，其中所述氨水浓度为2.0-10.0g/L。
优选的，步骤(2)的混合方式为将所述氟盐溶液、所述沉淀剂、所述络合剂及步骤(1)得到的所述混合盐溶液并流加入到所述碱性底液中，且加入过程中控制M离子加入量与氟离子加入量之比为(a+b)：3b，并控制混合液的pH为10.8-11.5，氨水浓度为2.0-10.0g/L。
优选的，步骤(2)中所述反应的反应温度为45-65℃。
优选的，步骤(2)中当检测到所述混合液中物料的D50达到2.0-11.0μm时，停止进料。
优选的，步骤(3)中所述固体产物还经过洗涤，干燥，过筛及除磁处理。
优选的，一种如上所述的镍钴锰酸锂正极材料前驱体的制备方法，包括以下步骤：
S1.按照所需镍、钴、锰、M元素的摩尔比例，即x：y：z：(a+b)，选用可溶性盐为原料，配制金属离子总浓度为1.0-2.0mol/L的混合盐溶液；
S2.配制浓度为0.01-1.0mol/L的氟化钠溶液；
S3.配制浓度为4.0-10.0mol/L的氢氧化钠溶液作为沉淀剂；
S4.配制浓度为6.0-12.0mol/L的氨水作为络合剂；
S5.向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为10.8-11.5，氨水浓度为2.0-10.0g/L)至漫过底层搅拌桨，启动搅拌；
S6.将混合盐溶液、氟化钠溶液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制混合盐溶液中M金属离子加入量与氟化钠加入量之比(a+b)：3b，并控制釜内反应温度为45-65℃，pH为10.8-11.5，氨水浓度为2.0-10.0g/L；
S7.当检测到反应釜内物料的D50达到2.0-11.0μm时，停止进料；
S8.将釜内物料进行固液分离，将固体产物用纯水洗涤后，在100-150℃下真空干燥2-3h；
S9.干燥料经过筛、除磁后即得到高电压镍钴锰酸锂正极材料前驱体。
一种镍钴锰酸锂正极材料前驱体，由如上所述的制备方法制备得到。
优选的，所述镍钴锰酸锂正极材料前驱体的化学通式为NixCoyMnzMa(OH)2+3a·bMF3，其中0<x<1，0<y<1，0<z<1，x+y+z＝1，0<a<0.01，0<b<0.01，M为Ho、Tm、Yb、Lu中的至少一种。
优选的，所述镍钴锰酸锂正极材料前驱体的相貌为球形或类球形。
优选的，所述镍钴锰酸锂正极材料前驱体的相貌为由一次颗粒团聚而成的二次颗粒，所述二次颗粒的粒度为2.0-11.0μm。
优选的，所述二次颗粒的内部及表层分布有粒径为10-200nm的晶粒。
优选的，所述晶粒为MF3。一种镍钴锰酸锂正极材料，由包括如上所述的镍钴锰酸锂正极材料前驱体的原料制得。
优选的，所述镍钴锰酸锂正极材料的化学通式为LiNixCoyMnzMaO2+1.5a·bMF3，其中0<x<1，0<y<1，0<z<1，x+y+z＝1，0<a<0.01，0<b<0.01，M为Ho、Tm、Yb、Lu中的至少一种。
优选的，所述镍钴锰酸锂正极材料的形貌为颗粒粒径为2.0-8.0μm的单晶颗粒。
一种如上所述的镍钴锰酸锂正极材料的制备方法，包括以下步骤：将所述镍钴锰酸锂正极材料前驱体和锂源混合，在氧气氛下进行一次烧结，再进行二次烧结，冷却，破碎，即得所述锂离子电池正极材料。
优选的，所述混合操作为按照镍钴锰元素与锂元素的摩尔比为1:(1.0-1.2)将所述镍钴锰酸锂正极材料前驱体和锂源混合。
优选的，所述锂源为碳酸锂、硝酸锂及草酸锂中的至少一种。
优选的，所述一次烧结为将所述所述镍钴锰酸锂正极材料前驱体和锂源混合后，在氧气氛下进行升温，升温速率为0.5-10℃/min，升温梯度为从室温升温至300-600℃，保温1-2h。
优选的，所述二次烧结为在一次烧结结束后继续升温至1050-1200℃，保温12-36h。
优选的，一种如上所述的镍钴锰酸锂正极材料的制备方法，包括以下步骤：
按照镍钴锰元素与锂元素的摩尔比为1:(1.0-1.2)，将上述镍钴锰酸锂正极材料前驱体与碳酸锂、硝酸锂、草酸锂中的至少一种混合后，在空气/氧气气氛下升温，升温速率为0.5-10℃/min，升温梯度为从室温升温至300-600℃，保温1-2h，继续升温至1050-1200℃，保温12-36h，之后经破碎、过筛、除铁，即得高电压镍钴锰酸锂正极材料。
一种电极，包括如上所述的镍钴锰酸锂正极材料。
一种电池，包括如上所述的电极。
本发明的有益效果是：
本发明的镍钴锰酸锂正极材料是首先通过共沉淀法制备得到高电压镍钴锰酸锂正极材料前驱体，再与锂源混合烧结后制得。由于镍钴锰酸锂正极材料中掺杂了镧系金属元素，并包覆镧系金属氟化物，能进一步提高材料在高电压下的循环稳定性。
其反应原理如下：
在共沉淀过程中：
xNi2++yCo2++zMn2++2OH-→NixCoyMnz(OH)2
M3++3OH-→M(OH)3
M3++3F-→MF3。
一方面，镧系金属离子与氢氧根反应生成氢氧化物，同时与镍钴锰氢氧化物反应形成共沉淀，得到掺杂镧系金属元素的镍钴锰氢氧化物前驱体，掺杂镧系金属元素能够进一步提高晶格稳定性，从而进一步提高后续正极材料的循环性能；另一方面，镧系金属离子与氟离子反应生成镧系金属氟化物沉淀，该沉淀以小晶粒的形式与镍钴锰氢氧化物前驱体混合，并附着在前驱体的内部及表层，在后续高温烧结正极材料时，可进一步熔化形成表面包覆层，解决了目前正极材料烧结时包覆剂需进行多次添加混料再烧结的问题，包覆能进一步提高材料的循环性能。
镧系金属氟化物高温易水解，首先在100-150℃下真空干燥2-3h，去除表面水，其次，在300-600℃保温1-2h，去除材料的结晶水，最后，在1050-1200℃下使氟化物熔 化，并保温为12-36h，烧结制备得到镍钴锰酸锂正极材料。
附图说明
图1为本发明实施例1的镍钴锰酸锂正极材料前驱体的SEM图；
图2为本发明实施例1的镍钴锰酸锂正极材料的SEM图；
图3为本发明对比例1的镍钴锰酸锂正极材料前驱体的SEM图。
具体实施方式
下面结合具体实施例对本发明做进一步的说明。
实施例1：
一种高电压镍钴锰酸锂正极材料前驱体的制备方法，包括如下步骤：
S1.按照所需Ni、Co、Mn、Ho元素的摩尔比例，即6.5：1：2.5：0.16，选用硫酸盐为原料，配制金属离子总浓度为1.0mol/L的混合盐溶液；
S2.配制浓度为0.01mol/L的氟化钠溶液；
S3.配制浓度为4.0mol/L的氢氧化钠溶液作为沉淀剂；
S4.配制浓度为6.0mol/L的氨水作为络合剂；
S5.向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为11.3，氨浓度为8.0g/L)至漫过底层搅拌桨，启动搅拌；
S6.将混合盐溶液、氟化钠溶液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制混合盐溶液中Ho金属离子加入量与氟化钠加入量之比2：3，并控制釜内反应温度为58℃，pH为11.3，氨浓度为8.0g/L；
S7.当检测到反应釜内物料的D50达到4.0μm时，停止进料；
S8.将釜内物料进行固液分离，将固体产物用纯水洗涤后，在140℃下真空干燥3h；
S9.干燥料经过筛、除磁后即得到高电压镍钴锰酸锂正极材料前驱体。
一种高电压镍钴锰酸锂正极材料前驱体，其由上述制备方法制备得到，其SEM图如图1所示，其化学式为Ni0.65Co0.1Mn0.25Ho0.008(OH)2.024·0.008HoF3，其形貌为球形或类球形，由一次颗粒团聚而成的二次颗粒，二次颗粒的粒度为4.0μm；球形颗粒内部及表层分布有小晶粒，小晶粒的粒径为10nm-200nm。
一种高电压镍钴锰酸锂正极材料，采用上述前驱体与锂源烧结制备而得，其SEM图如图2所示，其化学通式为LiNi0.65Co0.1Mn0.25Ho0.008O2.012·0.008MF3，其形貌为单晶颗粒，颗粒粒径为6.0μm。
一种高电压镍钴锰酸锂正极材料的制备方法，包括如下步骤：
按照镍钴锰元素与锂元素的摩尔比为1:1.2，将上述前驱体与硝酸锂混合后在氧气气氛下升温，升温速率为10℃/min，升温梯度为从室温升温至600℃保温1h，继续升温至1150℃保温为32h，之后经破碎、过筛、除铁，即得高电压镍钴锰酸锂正极材料。
实施例2：
一种高电压镍钴锰酸锂正极材料前驱体的制备方法，包括如下步骤：
S1.按照所需Ni、Co、Mn、Tm元素的摩尔比例，即6：2：2：0.1，选用硝酸盐为原料，配制金属离子总浓度为1.5mol/L的混合盐溶液；
S2.配制浓度为0.5.0mol/L的氟化钠溶液；
S3.配制浓度为8.0mol/L的氢氧化钠溶液作为沉淀剂；
S4.配制浓度为10.0mol/L的氨水作为络合剂；
S5.向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为11.1，氨浓度为6.0g/L)至漫过底层搅拌桨，启动搅拌；
S6.将混合盐溶液、氟化钠溶液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制混合盐溶液中Tm金属离子加入量与氟化钠加入量之比2：3，并控制釜内反应温度为55℃，pH为11.1，氨浓度为6.0g/L；
S7.当检测到反应釜内物料的D50达到7.0μm时，停止进料；
S8.将釜内物料进行固液分离，将固体产物用纯水洗涤后，在100℃下真空干燥3h；
S9.干燥料经过筛、除磁后即得到高电压镍钴锰酸锂正极材料前驱体。
一种高电压镍钴锰酸锂正极材料前驱体，其由上述制备方法制备得到，其化学式为Ni0.6Co0.2Mn0.2Tm0.005(OH)2.015·0.005TmF3，其形貌为球形或类球形，由一次颗粒团聚而成的二次颗粒，二次颗粒的粒度为7.0μm；球形颗粒内部及表层分布有小晶粒，小晶粒的粒径为10nm-200nm。
一种高电压镍钴锰酸锂正极材料，采用上述前驱体与锂源烧结制备而得，其化学通式为LiNi0.6Co0.2Mn0.2Tm0.005O2.0075·0.005MF3，其形貌为单晶颗粒，颗粒粒径为2.0μm。
一种高电压镍钴锰酸锂正极材料的制备方法，包括如下步骤：
按照镍钴锰元素与锂元素的摩尔比为1:1.1，将上述前驱体与碳酸锂混合后在空气气氛下升温，升温速率为0.5℃/min，升温梯度为从室温升温至300℃保温2h，继续升温至1200℃保温为12h，之后经破碎、过筛、除铁，即得高电压镍钴锰酸锂正极材料。
实施例3：
一种高电压镍钴锰酸锂正极材料前驱体的制备方法，包括如下步骤：
S1.按照所需Ni、Co、Mn、Yb元素的摩尔比例，即5：2：3：0.12，选用氯化盐为原料，配制金属离子总浓度为2.0mol/L的混合盐溶液；
S2.配制浓度为1.0mol/L的氟化钠溶液；
S3.配制浓度为10.0mol/L的氢氧化钠溶液作为沉淀剂；
S4.配制浓度为12.0mol/L的氨水作为络合剂；
S5.向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为10.8，氨浓度为2.0g/L)至漫过底层搅拌桨，启动搅拌；
S6.将混合盐溶液、氟化钠溶液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制混合盐溶液中Yb金属离子加入量与氟化钠加入量之比1：2，并控制釜内反应温度为45℃，pH为10.8，氨浓度为2.0g/L；
S7.当检测到反应釜内物料的D50达到11.0μm时，停止进料；
S8.将釜内物料进行固液分离，将固体产物用纯水洗涤后，在150℃下真空干燥2h；
S9.干燥料经过筛、除磁后即得到高电压镍钴锰酸锂正极材料前驱体。
一种高电压镍钴锰酸锂正极材料前驱体，其由上述制备方法制备得到，其化学式为Ni0.5Co0.2Mn0.3Yb0.004(OH)2.012·0.008YbF3，其形貌为球形或类球形，由一次颗粒团聚而成的二次颗粒，二次颗粒的粒度为11.0μm；球形颗粒内部及表层分布有小晶粒，小晶粒的粒径为10nm-200nm。
一种高电压镍钴锰酸锂正极材料，采用上述前驱体与锂源烧结制备而得，其化学通式为LiNi0.5Co0.2Mn0.3Yb0.004O2.006·0.008YbF3，其形貌为单晶颗粒，颗粒粒径为8μm。
一种高电压镍钴锰酸锂正极材料的制备方法，包括如下步骤：
按照镍钴锰元素与锂元素的摩尔比为1:1.0，将上述前驱体与草酸锂混合后在空气气氛下升温，升温速率为5℃/min，升温梯度为从室温升温至450℃保温1.5h，继续升温至1100℃保温为36h，之后经破碎、过筛、除铁，即得高电压镍钴锰酸锂正极材料。
对比例1：
一种镍钴锰酸锂正极材料前驱体的制备方法，包括如下步骤：
S1.按照所需Ni、Co、Mn元素的摩尔比例，即6.5：1：2.5，选用硫酸盐为原料，配制金属离子总浓度为1.0mol/L的混合盐溶液；
S2.配制浓度为4.0mol/L的氢氧化钠溶液作为沉淀剂；
S3.配制浓度为6.0mol/L的氨水作为络合剂；
S4.向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为11.3，氨浓 度为8.0g/L)至漫过底层搅拌桨，启动搅拌；
S5.将混合盐溶液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制釜内反应温度为58℃，pH为11.3，氨浓度为8.0g/L；
S6.当检测到反应釜内物料的D50达到4.0μm时，停止进料；
S7.将釜内物料进行固液分离，将固体产物用纯水洗涤后，在140℃下真空干燥3h；
S8.干燥料经过筛、除磁后即得到镍钴锰酸锂正极材料前驱体。
一种镍钴锰酸锂正极材料前驱体，其由上述制备方法制备得到，其SEM图如图3所示，其化学式为Ni0.65Co0.1Mn0.25(OH)2，其形貌为球形或类球形，由一次颗粒团聚而成的二次颗粒，二次颗粒的粒度为4.0μm。
一种镍钴锰酸锂正极材料，采用上述前驱体与锂源烧结制备而得，其化学通式为LiNi0.65Co0.1Mn0.25O2，其形貌为单晶颗粒，颗粒粒径为6.0μm。
一种镍钴锰酸锂正极材料的制备方法，包括如下步骤：
按照镍钴锰元素与锂元素的摩尔比为1:1.2，将上述前驱体与硝酸锂混合后在氧气气氛下升温，升温速率为10℃/min，升温梯度为从室温升温至600℃保温1h，继续升温至1150℃保温为32h，之后经破碎、过筛、除铁，即得镍钴锰酸锂正极材料。
对比例2：
一种镍钴锰酸锂正极材料前驱体的制备方法，包括如下步骤：
S1.按照所需Ni、Co、Mn元素的摩尔比例，即6：2：2，选用硝酸盐为原料，配制金属离子总浓度为1.5mol/L的混合盐溶液；
S2.配制浓度为8.0mol/L的氢氧化钠溶液作为沉淀剂；
S3.配制浓度为10.0mol/L的氨水作为络合剂；
S4.向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为11.1，氨浓度为6.0g/L)至漫过底层搅拌桨，启动搅拌；
S5.将混合盐溶液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制釜内反应温度为55℃，pH为11.1，氨浓度为6.0g/L；
S6.当检测到反应釜内物料的D50达到7.0μm时，停止进料；
S7.将釜内物料进行固液分离，将固体产物用纯水洗涤后，在100℃下真空干燥3h；
S8.干燥料经过筛、除磁后即得到镍钴锰酸锂正极材料前驱体。
一种镍钴锰酸锂正极材料前驱体，其由上述制备方法制备得到，其化学式为Ni0.6Co0.2Mn0.2(OH)2，其形貌为球形或类球形，由一次颗粒团聚而成的二次颗粒，二次 颗粒的粒度为7.0μm。
一种镍钴锰酸锂正极材料，采用上述前驱体与锂源烧结制备而得，其化学通式为LiNi0.6Co0.2Mn0.2O2，其形貌为单晶颗粒，颗粒粒径为2.0μm。
一种镍钴锰酸锂正极材料的制备方法，包括如下步骤：
按照镍钴锰元素与锂元素的摩尔比为1:1.1，将上述前驱体与碳酸锂混合后在空气气氛下升温，升温速率为0.5℃/min，升温梯度为从室温升温至300℃保温2h，继续升温至1200℃保温为12h，之后经破碎、过筛、除铁，即得镍钴锰酸锂正极材料。
对比例3：
一种镍钴锰酸锂正极材料前驱体的制备方法，包括如下步骤：
S1.按照所需Ni、Co、Mn元素的摩尔比例，即5：2：3，选用氯化盐为原料，配制金属离子总浓度为2.0mol/L的混合盐溶液；
S2.配制浓度为10.0mol/L的氢氧化钠溶液作为沉淀剂；
S3.配制浓度为12.0mol/L的氨水作为络合剂；
S4.向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为10.8，氨浓度为2.0g/L)至漫过底层搅拌桨，启动搅拌；
S5.将混合盐溶液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制釜内反应温度为45℃，pH为10.8，氨浓度为2.0g/L；
S6.当检测到反应釜内物料的D50达到11.0μm时，停止进料；
S7.将釜内物料进行固液分离，将固体产物用纯水洗涤后，在150℃下真空干燥2h；
S8.干燥料经过筛、除磁后即得到镍钴锰酸锂正极材料前驱体。
一种镍钴锰酸锂正极材料前驱体，其由上述制备方法制备得到，其化学式为Ni0.5Co0.2Mn0.3(OH)2，其形貌为球形或类球形，由一次颗粒团聚而成的二次颗粒，二次颗粒的粒度为11.0μm。
一种镍钴锰酸锂正极材料，采用上述前驱体与锂源烧结制备而得，其化学通式为LiNi0.5Co0.2Mn0.3O2，其形貌为单晶颗粒，颗粒粒径为8μm。
一种镍钴锰酸锂正极材料的制备方法，包括如下步骤：
按照镍钴锰元素与锂元素的摩尔比为1:1.0，将上述前驱体与草酸锂混合后在空气气氛下升温，升温速率为5℃/min，升温梯度为从室温升温至450℃保温1.5h，继续升温至1100℃保温为36h，之后经破碎、过筛、除铁，即得镍钴锰酸锂正极材料。
试验例：
将实施例1-3及对比例1-3的正极材料配成扣式电池进行锂离子电池电化学性能测试，其具体步骤为：以N-甲基吡咯烷酮为溶剂，按照质量比9.2︰0.5︰0.3的比例将正极材料与乙炔黑、PVDF混合均匀，涂覆于铝箔上，经80℃鼓风干燥8h后，于120℃真空干燥12h。在氩气保护的手套箱中装配电池，负极为金属锂片，隔膜为聚丙烯膜，电解液为1M LiPF6-EC/DMC(1︰1，v/v)，采用2032型扣式电池壳在氩气保护的手套箱中组装成扣式电池，然后在25℃下3.0-4.5V进行电化学性能测试。
测试结果如表1所示。
表1：电池电性能测试结果
由表1可知，本发明的高电压镍钴锰酸锂正极材料在高电压下具有较好的放电容量及循环稳定性，其0.1C放电容量在185.7mAh/g以上，其100次循环后放电比容量在169.7mAh/g以上，循环保持率在90.1％以上，同时分别对比实施例1与对比例1、实施例2与对比例2以及实施例3与对比例3可知，在制备镍钴锰酸锂正极材料前驱体的过程中不加入镧系金属元素时，最终制得的镍钴锰酸锂正极材料在高压下的0.1C放电容量、100次循环后放电比容量及循环保持率均会下降。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种镍钴锰酸锂正极材料前驱体的制备方法，其特征在于：包括以下步骤：
    (1)配制含镍、钴、锰及M元素的可溶性的混合盐溶液，所述M元素为Ho、Tm、Yb、Lu中的至少一种；
    (2)将氟盐溶液、沉淀剂、络合剂及步骤(1)得到的混合盐溶液与碱性底液混合进行反应，得到混合液；
    (3)将步骤(2)得到的混合液进行固液分离，得到固体产物即为所述镍钴锰酸锂正极材料前驱体。
  2. 一种镍钴锰酸锂正极材料前驱体，其特征在于：由权利要求1所述的制备方法制备得到。
  3. 根据权利要求2所述的镍钴锰酸锂正极材料前驱体，其特征在于：所述镍钴锰酸锂正极材料前驱体的化学通式为NixCoyMnzMa(OH)2+3a·bMF3，其中0<x<1，0<y<1，0<z<1，x+y+z＝1，0<a<0.01，0<b<0.01。
  4. 根据权利要求3所述的镍钴锰酸锂正极材料前驱体，其特征在于：所述镍钴锰酸锂正极材料前驱体的相貌为由一次颗粒团聚而成的二次颗粒，所述二次颗粒的粒度为2.0-11.0μm。
  5. 根据权利要求4所述的镍钴锰酸锂正极材料前驱体，其特征在于：所述二次颗粒的内部及表层分布有粒径为10-200nm的晶粒。
  6. 一种镍钴锰酸锂正极材料，其特征在于：由包括权利要求2-5任一项所述的镍钴锰酸锂正极材料前驱体的原料制得。
  7. 根据权利要求6所述的镍钴锰酸锂正极材料，其特征在于：所述镍钴锰酸锂正极材料的化学通式为LiNixCoyMnzMaO2+1.5a·bMF3，其中0<x<1，0<y<1，0<z<1，x+y+z＝1，0<a<0.01，0<b<0.01。
  8. 权利要求6-7任一项所述的镍钴锰酸锂正极材料的制备方法，其特征在于：包括以下步骤：将所述镍钴锰酸锂正极材料前驱体和锂源混合，在氧气氛下进行一次烧结，再进行二次烧结，冷却，破碎，即得所述锂离子电池正极材料。
  9. 一种电极，其特征在于：包括权利要求6-7任一项所述的镍钴锰酸锂正极材料。
  10. 一种电池，其特征在于：包括权利要求9所述的电极。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016139583A (ja) * 2015-01-29 2016-08-04 輔仁大學學校財團法人輔仁大學 リチウムイオン電池の金属勾配ドープ正極材料
CN109461925A (zh) * 2018-06-29 2019-03-12 北京当升材料科技股份有限公司 一种单晶镍钴锰酸锂正极材料、前驱体及其制备方法
CN110048118A (zh) * 2019-04-15 2019-07-23 金驰能源材料有限公司 一种高镍型镍钴锰酸锂单晶前驱体及其制备方法和高镍型镍钴锰酸锂单晶正极材料
CN112164790A (zh) * 2020-08-27 2021-01-01 荆门市格林美新材料有限公司 包覆型锂电池用前驱体、锂电池正极材料及其制备方法
CN113793923A (zh) * 2021-08-13 2021-12-14 恒大新能源技术(深圳)有限公司 共掺杂三元正极前驱体及其制备方法、三元正极材料、二次电池
US20210408537A1 (en) * 2018-11-20 2021-12-30 Lg Chem, Ltd. Positive Electrode Active Material for Lithium Secondary Battery and Method of Preparing the Same
CN114162881A (zh) * 2021-11-26 2022-03-11 中国长江三峡集团有限公司 一种阴离子原位掺杂高镍三元正极材料的制备方法
CN114804235A (zh) * 2022-05-26 2022-07-29 广东邦普循环科技有限公司 一种高电压镍钴锰酸锂正极材料及其制备方法和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103490051B (zh) * 2013-09-18 2015-10-28 成都晶元新材料技术有限公司 一种适用于高电压的多元正极锂电材料及其制备方法
CN114122380A (zh) * 2021-11-22 2022-03-01 合肥国轩高科动力能源有限公司 锆掺杂氟化铈包覆镍钴锰三元正极材料的制备方法、制得的正极材料

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016139583A (ja) * 2015-01-29 2016-08-04 輔仁大學學校財團法人輔仁大學 リチウムイオン電池の金属勾配ドープ正極材料
CN109461925A (zh) * 2018-06-29 2019-03-12 北京当升材料科技股份有限公司 一种单晶镍钴锰酸锂正极材料、前驱体及其制备方法
US20210408537A1 (en) * 2018-11-20 2021-12-30 Lg Chem, Ltd. Positive Electrode Active Material for Lithium Secondary Battery and Method of Preparing the Same
CN110048118A (zh) * 2019-04-15 2019-07-23 金驰能源材料有限公司 一种高镍型镍钴锰酸锂单晶前驱体及其制备方法和高镍型镍钴锰酸锂单晶正极材料
CN112164790A (zh) * 2020-08-27 2021-01-01 荆门市格林美新材料有限公司 包覆型锂电池用前驱体、锂电池正极材料及其制备方法
CN113793923A (zh) * 2021-08-13 2021-12-14 恒大新能源技术(深圳)有限公司 共掺杂三元正极前驱体及其制备方法、三元正极材料、二次电池
CN114162881A (zh) * 2021-11-26 2022-03-11 中国长江三峡集团有限公司 一种阴离子原位掺杂高镍三元正极材料的制备方法
CN114804235A (zh) * 2022-05-26 2022-07-29 广东邦普循环科技有限公司 一种高电压镍钴锰酸锂正极材料及其制备方法和应用

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