WO2023093142A1 - 一种高电压钴酸锂正极材料的制备方法 - Google Patents

一种高电压钴酸锂正极材料的制备方法 Download PDF

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WO2023093142A1
WO2023093142A1 PCT/CN2022/113436 CN2022113436W WO2023093142A1 WO 2023093142 A1 WO2023093142 A1 WO 2023093142A1 CN 2022113436 W CN2022113436 W CN 2022113436W WO 2023093142 A1 WO2023093142 A1 WO 2023093142A1
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particle size
doped
cobalt
large particle
positive electrode
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French (fr)
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许开华
张爱青
曹果林
金倬敏
李炳忠
杨克涛
史齐勇
谢金德
马兴兴
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格林美（江苏）钴业股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of preparation of high-voltage lithium cobaltate cathode materials, in particular to a preparation method of high-voltage lithium cobaltate cathode materials.
  • Lithium cobalt oxide cathode material has the characteristics of large specific capacity, high energy density, high working voltage platform, good cycle performance, and long life. It is mainly used in the 3C digital field. With the upgrading of digital products, lithium cobalt oxide is developing in the direction of high voltage, high compaction, and fast charging and discharging.
  • LiCoO2 cathode materials mainly focus on the development of products with higher charging voltage, higher energy density, longer cycle life and acceptable low cost and safety level.
  • Increasing the charge cut-off voltage can maximize the capacity of lithium cobalt oxide, but the LiCoO2 lattice structure will collapse when the material is charged and discharged, and the cycle stability and rate performance will be reduced.
  • LiCoO2 cathode materials The microstructure and macroscopic properties of lithium-ion battery cathode materials are obviously affected by the synthesis method, and there are great differences in the morphology, structure and electrochemical performance of materials under different synthesis methods.
  • the most widely used synthesis methods in the synthesis of LiCoO2 cathode materials include high-temperature solid-phase method, wet chemical method, and spray drying method.
  • the high-temperature solid-phase synthesis of LiCoO 2 is usually based on carbonates, nitrates, acetates, oxides or hydroxides of lithium and cobalt, which are fully mixed and then calcined at 900-1050°C in an air atmosphere.
  • atoms or ions pass through the interface between the various phases and pass through the phase regions to form the mutual diffusion of atoms or ions.
  • the driving force of the entire reaction is the difference in free energy between the reactant and the product.
  • the important factors affecting the reaction rate are: (1) the contact area and surface area between the reacting solid particles; (2) the nucleation rate of the product phase; (3) The diffusion rate of atoms or ions through each phase, especially through the product phase.
  • the high-temperature solid-phase method is simple and easy to control, and is suitable for industrial production, but it also has disadvantages such as large restrictions on raw materials, high energy consumption, and long reaction time.
  • wet chemical method is a general term for a series of material synthesis methods such as co-precipitation method, sol-gel method, and hydrothermal method; compared with high-temperature solid-phase method, the reaction of this type of synthetic material belongs to the atomic or molecular level, which can effectively control the composition of the product.
  • Morphology, composition and microstructure the synthesized material has the characteristics of high crystallinity, uniform particle size and large specific surface area.
  • the primary particle size of the precursor prepared by this type of method is fine, and the materials are evenly mixed, so the heat treatment temperature can be reduced, the time can also be shortened, and the energy consumption is greatly reduced.
  • Spray drying method is currently the most effective and commonly used method for synthesizing spherical materials. Its process can be described as follows: the raw materials are prepared into a solution or slurry, atomized and dispersed into uniform droplets by an atomizer, and brought into a liquid with a certain temperature by the airflow. In the cavity, a series of physical and chemical reactions such as solvent evaporation, solute nucleation, drying, thermal decomposition, etc. are quickly completed, and finally the required materials are sintered. This method can realize heat and mass transfer in a short time, avoiding the complicated process of mixing, drying, and crushing again.
  • the synthesized material has good sphericity, controllable particle size and uniform distribution, which is conducive to improving the tap density of the material. .
  • Doping is mainly a modification method that replaces some elements in the material components with various elements to form a homogeneous solid solution, aiming at stabilizing the structure of the material, thereby improving its electrochemical performance and thermal stability, but sometimes Some capacity will be sacrificed.
  • the advantage of solid-phase doping is simplicity and convenience, but the disadvantage is unevenness.
  • the present invention provides a method for preparing a high-voltage lithium cobalt oxide positive electrode material, which can make LiCoO 2 solid-phase doped evenly, improve the compaction density and processability of the high-voltage lithium cobalt oxide positive electrode material, Effectively improve the structural stability of the material, and improve the cycle performance and rate performance of the battery.
  • a method for preparing a high-voltage lithium cobaltate positive electrode material characterized in that it comprises the following steps:
  • Step 1 Preparation of doped tricobalt tetroxide
  • Step 1.1 Preparation of doped cobaltous hydroxide
  • cobalt-containing solution as cobalt source, sodium hydroxide as precipitating agent, ammonia water or EDTA solution as complexing agent, nitrogen or argon as protective gas, hydrazine hydrate solution or ascorbic acid as reducing agent, mix the compound doped with metal M, and use Batch reaction kettle, by controlling the number of crystal nuclei in the initial stage of synthesis, respectively controlling the pH value at 10.5-11, 9.5-10, and performing wet synthesis, the obtained doped cobaltous hydroxide is respectively recorded as small particle size doped type Cobaltous hydroxide, large particle size doped cobaltous hydroxide;
  • Step 1.2 Preparation of cobalt oxyhydroxide
  • the hydrogen peroxide solution is used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively, and the obtained doped cobalt oxyhydroxides are respectively recorded as small particle size doped Type cobalt oxyhydroxide, large particle size doped cobalt oxyhydroxide;
  • the obtained doped tricobalt tetroxide (Co 1-x M x ) 3 O 4 has a particle size of 3 Small particle size doped cobalt tetroxide with a particle size of -5 ⁇ m, and large particle size doped cobalt tetraoxide with a particle size of 10-15 ⁇ m;
  • the small particle size doped tricobalt tetroxide and the large particle size doped tricobalt tetroxide are mixed with battery grade lithium carbonate respectively, sintered, cooled, pulverized, and sieved to obtain the doped lithium cobaltate LiCo 1-x M x O 2 respectively It is recorded as small particle size doped lithium cobalt oxide and large particle size doped lithium cobalt oxide; where, x ⁇ 0.005;
  • Step 3 Mixing the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide according to a set mass ratio to obtain a high voltage lithium cobalt oxide positive electrode material.
  • the doping metal M is one or more of Al, Ni, Mg, and Mn.
  • the ion concentration of the doping metal M is controlled at 500-5000 ppm.
  • the cobalt-containing solution is one or more of cobalt nitrate, cobalt chloride, cobalt sulfate, and cobalt oxalate solutions, and the concentration of the cobalt-containing solution is 80-200g/L,
  • the temperature is controlled at 50-70° C.
  • the flow rate of the protective gas is controlled at 5 L/min
  • the amount of the reducing agent accounts for 0.02%-0.1% of the solution.
  • the pH value is controlled at 9.5-11, and the concentration of the hydrogen peroxide solution is 10%-15%.
  • the temperature of the calcination process is controlled at 1000-1050°C
  • the lithium-cobalt ratio is controlled at 1.0-1.1
  • the holding time is controlled at 10-20h.
  • step 1.3 the tap density of the doped tricobalt tetroxide is greater than 2.0 g/cm 3 , the specific surface area is 3.0-5.0 m 2 /g, and the shape is spherical or quasi-spherical.
  • the mixing includes: mixing the small-grain-doped cobalt tetroxide and the large-grain doped cobalt tetroxide with battery-grade lithium carbonate in a high-speed mixer for 30-60 minutes;
  • the sintering includes: placing the mixture in a sagger, then putting it into a muffle furnace, raising the temperature to 1000-1050°C at a heating rate of 5-10°C/min and keeping it warm for 10-20h, and continuously feeding air during the sintering process , the flow of air is controlled at 5-10L/min;
  • the cooling includes: cooling the sintered product to room temperature;
  • the pulverization includes: coarsely pulverizing the sintered product with a mortar, and then pouring the coarsely pulverized sintered product into a universal pulverizer for fine pulverization;
  • the sieving includes: pouring the pulverized sintered product into a 200-mesh sieve for sieving treatment.
  • the set mass ratio is (5:5)-(8:2).
  • step 3 the set mass ratio is 7:3 or 8:2.
  • the present invention obtains doped tricobalt tetroxide with controllable particle size of one or more elements in Al, Ni, Mg and Mn through wet synthesis, oxidation and calcination, and the small particle size doped tricobalt tetroxide, large
  • the particle size-doped cobalt tetroxide is mixed with battery-grade lithium carbonate, sintered, cooled, crushed, and sieved to realize wet doping of the precursor, so that the doping elements are evenly distributed at the atomic level, and particle sizes of 6-7 ⁇ m,
  • the 12-18 ⁇ m doped lithium cobalt oxide has high purity and no impurity phase, which solves the technical problem of uneven doping of the existing LiCoO 2 solid phase.
  • the present invention mixes the prepared small particle size doped lithium cobaltate and large particle size doped lithium cobaltate according to the set mass ratio, which greatly improves the compaction density and processability of the high voltage lithium cobaltate positive electrode material. performance, effectively improving the structural stability of the material, and improving the cycle performance and rate performance of the battery.
  • the present invention can stabilize structure by doping Al, Mn, and reduce production cost;
  • Doping Mg can improve the ionic conductivity of material, is conducive to the rate performance that promotes lithium cobalt oxide cathode material;
  • Doping Ni can improve cobalt The capacity of the lithium acid cathode material does not affect the rate performance, and the price of Ni is low, which can reduce the production cost
  • Fig. 1 is a flow chart of the preparation method of the high-voltage lithium cobaltate positive electrode material of the present invention.
  • the preparation method of the high-voltage lithium cobaltate cathode material of the present invention comprises the following steps:
  • Step 1 Preparation of doped tricobalt tetroxide
  • Step 1.1 Preparation of doped cobaltous hydroxide
  • cobalt-containing solution as cobalt source, sodium hydroxide as precipitating agent, ammonia water or EDTA solution as complexing agent, nitrogen or argon as protective gas, hydrazine hydrate solution or ascorbic acid as reducing agent, mix the compound doped with metal M, and use Batch reaction kettle, by controlling the number of crystal nuclei in the initial stage of synthesis, respectively controlling the pH value at 10.5-11, 9.5-10, and performing wet synthesis, the obtained doped cobaltous hydroxide is respectively recorded as small particle size doped type Cobaltous hydroxide, large particle size doped cobaltous hydroxide.
  • the doping metal M is one or more of Al, Ni, Mg, and Mn.
  • doping Al and Mn can stabilize the structure and reduce production costs; the radius of Mg is close to that of Co, and doping Mg can improve the ionic conductivity of the material, which is conducive to improving the rate performance of lithium cobaltate cathode materials; doping Ni can While improving the capacity of the lithium cobalt oxide positive electrode material, the rate performance is not affected, and the price of Ni is low, which can reduce the production cost.
  • the ion concentration of doping metal M is controlled at 500-5000ppm.
  • the cobalt-containing solution is one or more of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt oxalate solution, the concentration of the cobalt-containing solution is 80-200g/L, and the temperature in the wet synthesis process is controlled at 50-70°C, the flow rate of protective gas is controlled at 5L/min, and the amount of reducing agent accounts for 0.02%-0.1% of the solution.
  • Step 1.2 Preparation of cobalt oxyhydroxide
  • the hydrogen peroxide solution is used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively, and the obtained doped cobalt oxyhydroxides are respectively recorded as small particle size doped Type cobalt oxyhydroxide, large particle size doped cobalt oxyhydroxide.
  • the pH value is controlled at 9.5-11, and the concentration of the hydrogen peroxide solution is 10%-15%.
  • the obtained doped tricobalt tetroxide (Co 1-x M x ) 3 O 4 has a particle size of 3 Small particle size doped cobalt tetroxide with a particle size of -5 ⁇ m, and large particle size doped cobalt tetraoxide with a particle size of 10-15 ⁇ m.
  • the temperature is controlled at 1000-1050°C
  • the lithium-cobalt ratio is controlled at 1.0-1.1
  • the holding time is controlled at 10-20h.
  • the tap density of the doped cobalt tetroxide obtained in step 1.3 is greater than 2.0 g/cm 3 , the specific surface area is 3.0-5.0 m 2 /g, and the shape is spherical or quasi-spherical.
  • the small particle size doped tricobalt tetroxide and the large particle size doped tricobalt tetroxide are mixed with battery grade lithium carbonate respectively, sintered, cooled, pulverized, and sieved to obtain the doped lithium cobaltate LiCo 1-x M x O 2 respectively It is recorded as small particle size doped lithium cobalt oxide and large particle size doped lithium cobalt oxide; wherein, x ⁇ 0.005.
  • the mixing includes: mixing the small-grain-doped cobalt tetroxide and the large-grain doped cobalt tetroxide with battery-grade lithium carbonate in a high-speed mixer for 30-60 minutes;
  • the sintering includes: placing the mixture in a sagger, then putting it into a muffle furnace, raising the temperature to 1000-1050°C at a heating rate of 5-10°C/min and keeping it warm for 10-20h, and continuously feeding air during the sintering process , the flow of air is controlled at 5-10L/min;
  • the cooling includes: cooling the sintered product to room temperature;
  • the pulverization includes: coarsely pulverizing the sintered product with a mortar, and then pouring the coarsely pulverized sintered product into a universal pulverizer for fine pulverization;
  • the sieving includes: pouring the pulverized sintered product into a 200-mesh sieve for sieving treatment.
  • Step 3 Mixing the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide according to a set mass ratio to obtain a high voltage lithium cobalt oxide positive electrode material.
  • the mass ratio set in the present invention is (5:5)-(8:2). Preferably, the set mass ratio is 7:3 or 8:2.
  • cobalt nitrate solution with a concentration of 80g/L as the cobalt source, sodium hydroxide as the precipitant, ammonia solution as the complexing agent, nitrogen as the protective gas, and hydrazine hydrate solution as the reducing agent, mix the compound doped with metal Al, and use intermittent Type reaction kettle, control the ion concentration of doped metal Al at 500ppm, the temperature at 50°C, the flow rate of protective gas at 5L/min, and the amount of reducing agent accounted for 0.02% of the solution.
  • the pH values are respectively controlled at 10.5-11 and 9.5-10, and wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 9.5 and a concentration of 10% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1000°C, a lithium-cobalt ratio of 1.0, and a holding time of 10 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and the large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 30 minutes; The heating rate per minute was raised to 1000°C and held for 10 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 5L/min; then the sintered product was cooled to room temperature, and then the sintered product was coarsely pulverized with a mortar.
  • the sintered product is poured into a universal pulverizer for fine crushing, and the finely crushed sintered product is poured into a 200-mesh sieve for sieving treatment to obtain small-sized doped lithium cobaltate with a particle size of 6-7 ⁇ m, particle size Large particle size doped lithium cobalt oxide in 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 5:5 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt chloride solution with a concentration of 140g/L as the cobalt source, sodium hydroxide as the precipitant, EDTA solution as the complexing agent, argon as the protective gas, and ascorbic acid as the reducing agent, mix the compound doped with metal Al, and use intermittent Type reactor, control the ion concentration of doped metal Al at 2000ppm, the temperature at 60°C, the flow rate of protective gas at 5L/min, and the amount of reducing agent accounted for 0.06% of the solution.
  • the pH values are respectively controlled at 10.5-11 and 9.5-10, and wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 10 and a concentration of 12.5% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1025°C, a lithium-cobalt ratio of 1.05, and a holding time of 15 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 45 minutes; The heating rate per minute was raised to 1025°C and kept for 15 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 7.5L/min. Then the sintered product was cooled to room temperature, and then the sintered product was coarsely pulverized with a mortar.
  • the pulverized sintered product is poured into a universal pulverizer for fine crushing, and the finely pulverized sintered product is poured into a 200-mesh screen for sieving treatment to obtain small particle size doped lithium cobaltate with a particle size of 6-7 ⁇ m, Large particle size doped lithium cobalt oxide with a particle size of 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 7:3 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt sulfate solution with a concentration of 200g/L as the cobalt source, sodium hydroxide as the precipitating agent, EDTA solution as the complexing agent, argon as the protective gas, and ascorbic acid as the reducing agent, mix the compound doped with metal Al, and use the batch method
  • the ion concentration of doped metal Al is controlled at 5000ppm
  • the temperature is at 70°C
  • the flow rate of the protective gas is at 5L/min
  • the amount of reducing agent used is 0.1% of the solution.
  • the pH value is controlled at 10.5-11 and 9.5-10, and the wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 11 and a concentration of 15% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1050°C, a lithium-cobalt ratio of 1.1, and a holding time of 20 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and the large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 60 minutes; The heating rate per minute was raised to 1050°C and held for 20 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 10L/min. Then the sintered product was cooled to room temperature, and the sintered product was coarsely pulverized with a mortar.
  • the sintered product is poured into a universal pulverizer for fine crushing, and the finely crushed sintered product is poured into a 200-mesh sieve for sieving treatment to obtain small-sized doped lithium cobaltate with a particle size of 6-7 ⁇ m, particle size Large particle size doped lithium cobalt oxide in 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 8:2 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt nitrate solution with a concentration of 80g/L as the cobalt source, sodium hydroxide as the precipitant, ammonia solution as the complexing agent, nitrogen as the protective gas, and hydrazine hydrate solution as the reducing agent, mix the compound doped with metal Ni, and use intermittent Type reaction kettle, control the ion concentration of doped metal Ni at 500ppm, the temperature at 50°C, the flow rate of protective gas at 5L/min, and the amount of reducing agent accounted for 0.02% of the solution.
  • the pH values are respectively controlled at 10.5-11 and 9.5-10, and wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 9.5 and a concentration of 10% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1000°C, a lithium-cobalt ratio of 1.0, and a holding time of 10 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and the large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 30 minutes; The heating rate per minute was raised to 1000°C and held for 10 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 5L/min; then the sintered product was cooled to room temperature, and then the sintered product was coarsely pulverized with a mortar.
  • the sintered product is poured into a universal pulverizer for fine crushing, and the finely crushed sintered product is poured into a 200-mesh sieve for sieving treatment to obtain small-sized doped lithium cobaltate with a particle size of 6-7 ⁇ m, particle size Large particle size doped lithium cobalt oxide in 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 5:5 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt chloride solution with a concentration of 140g/L as the cobalt source, sodium hydroxide as the precipitant, EDTA solution as the complexing agent, argon as the protective gas, and ascorbic acid as the reducing agent, mix the compound doped with metal Ni, and use intermittent Type reactor, the ion concentration of doped metal Ni is controlled at 2000ppm, the temperature is at 60°C, the flow rate of protective gas is at 5L/min, and the amount of reducing agent accounts for 0.06% of the solution.
  • the pH values are respectively controlled at 10.5-11 and 9.5-10, and wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 10 and a concentration of 12.5% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1025°C, a lithium-cobalt ratio of 1.05, and a holding time of 15 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 45 minutes; The heating rate per minute was raised to 1025°C and kept for 15 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 7.5L/min. Then the sintered product was cooled to room temperature, and then the sintered product was coarsely pulverized with a mortar.
  • the pulverized sintered product is poured into a universal pulverizer for fine crushing, and the finely pulverized sintered product is poured into a 200-mesh screen for sieving treatment to obtain small particle size doped lithium cobaltate with a particle size of 6-7 ⁇ m, Large particle size doped lithium cobalt oxide with a particle size of 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 7:3 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt sulfate solution with a concentration of 200g/L as the cobalt source, sodium hydroxide as the precipitating agent, EDTA solution as the complexing agent, argon as the protective gas, and ascorbic acid as the reducing agent, mix the compound doped with metal Ni, and use the batch method
  • the ion concentration of doped metal Ni is controlled at 5000ppm
  • the temperature is at 70°C
  • the flow rate of the protective gas is at 5L/min
  • the amount of reducing agent used is 0.1% of the solution.
  • the pH value is controlled at 10.5-11 and 9.5-10, and the wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 11 and a concentration of 15% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1050°C, a lithium-cobalt ratio of 1.1, and a holding time of 20 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and the large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 60 minutes; The heating rate per minute was raised to 1050°C and held for 20 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 10L/min. Then the sintered product was cooled to room temperature, and the sintered product was coarsely pulverized with a mortar.
  • the sintered product is poured into a universal pulverizer for fine crushing, and the finely crushed sintered product is poured into a 200-mesh sieve for sieving treatment to obtain small-sized doped lithium cobaltate with a particle size of 6-7 ⁇ m, particle size Large particle size doped lithium cobalt oxide in 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 8:2 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt nitrate solution with a concentration of 80g/L as the cobalt source, sodium hydroxide as the precipitant, ammonia solution as the complexing agent, nitrogen as the protective gas, and hydrazine hydrate solution as the reducing agent, mix the compound doped with metal Mg, and use intermittent Type reaction kettle, control the ion concentration of doped metal Mg at 500ppm, the temperature at 50°C, the flow rate of protective gas at 5L/min, and the amount of reducing agent accounted for 0.02% of the solution.
  • the pH values are respectively controlled at 10.5-11 and 9.5-10, and wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 9.5 and a concentration of 10% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1000°C, a lithium-cobalt ratio of 1.0, and a holding time of 10 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and the large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 30 minutes; The heating rate per minute was raised to 1000°C and held for 10 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 5L/min; then the sintered product was cooled to room temperature, and then the sintered product was coarsely pulverized with a mortar.
  • the sintered product is poured into a universal pulverizer for fine crushing, and the finely crushed sintered product is poured into a 200-mesh sieve for sieving treatment to obtain small-sized doped lithium cobaltate with a particle size of 6-7 ⁇ m, particle size Large particle size doped lithium cobalt oxide in 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 5:5 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt chloride solution with a concentration of 140g/L as the cobalt source, sodium hydroxide as the precipitant, EDTA solution as the complexing agent, argon as the protective gas, and ascorbic acid as the reducing agent, mix the compound doped with metal Mg, and use intermittent Type reaction kettle, control the ion concentration of doped metal Mg at 2000ppm, the temperature at 60°C, the flow rate of protective gas at 5L/min, and the amount of reducing agent accounted for 0.06% of the solution.
  • the pH values are respectively controlled at 10.5-11 and 9.5-10, and wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 10 and a concentration of 12.5% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1025°C, a lithium-cobalt ratio of 1.05, and a holding time of 15 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 45 minutes; The heating rate per minute was raised to 1025°C and kept for 15 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 7.5L/min. Then the sintered product was cooled to room temperature, and then the sintered product was coarsely pulverized with a mortar.
  • the pulverized sintered product is poured into a universal pulverizer for fine crushing, and the finely pulverized sintered product is poured into a 200-mesh screen for sieving treatment to obtain small particle size doped lithium cobaltate with a particle size of 6-7 ⁇ m, Large particle size doped lithium cobalt oxide with a particle size of 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 7:3 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt sulfate solution with a concentration of 200g/L as the cobalt source, sodium hydroxide as the precipitant, EDTA solution as the complexing agent, argon as the protective gas, and ascorbic acid as the reducing agent, mix the compound doped with metal Mg, and use the batch method
  • the ion concentration of doped metal Mg is controlled at 5000ppm
  • the temperature is at 70°C
  • the flow rate of the protective gas is at 5L/min
  • the amount of reducing agent accounts for 0.1% of the solution.
  • the pH value is controlled at 10.5-11 and 9.5-10, and the wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 11 and a concentration of 15% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1050°C, a lithium-cobalt ratio of 1.1, and a holding time of 20 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and the large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 60 minutes; The heating rate per minute was raised to 1050°C and held for 20 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 10L/min. Then the sintered product was cooled to room temperature, and the sintered product was coarsely pulverized with a mortar.
  • the sintered product is poured into a universal pulverizer for fine crushing, and the finely crushed sintered product is poured into a 200-mesh sieve for sieving treatment to obtain small-sized doped lithium cobaltate with a particle size of 6-7 ⁇ m, particle size Large particle size doped lithium cobalt oxide in 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 8:2 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt nitrate solution with a concentration of 80g/L as the cobalt source, sodium hydroxide as the precipitant, ammonia solution as the complexing agent, nitrogen as the protective gas, and hydrazine hydrate solution as the reducing agent, mix the compound doped with metal Mn, and use intermittent Type reaction kettle, control the ion concentration of doped metal Mn at 500ppm, the temperature at 50°C, the flow rate of protective gas at 5L/min, and the amount of reducing agent accounted for 0.02% of the solution.
  • the pH values are respectively controlled at 10.5-11 and 9.5-10, and wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 9.5 and a concentration of 10% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1000°C, a lithium-cobalt ratio of 1.0, and a holding time of 10 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and the large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 30 minutes; The heating rate per minute was raised to 1000°C and held for 10 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 5L/min; then the sintered product was cooled to room temperature, and then the sintered product was coarsely pulverized with a mortar.
  • the sintered product is poured into a universal pulverizer for fine crushing, and the finely crushed sintered product is poured into a 200-mesh sieve for sieving treatment to obtain small-sized doped lithium cobaltate with a particle size of 6-7 ⁇ m, particle size Large particle size doped lithium cobalt oxide in 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 5:5 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt chloride solution with a concentration of 140g/L as the cobalt source, sodium hydroxide as the precipitant, EDTA solution as the complexing agent, argon as the protective gas, and ascorbic acid as the reducing agent, mix the compound doped with metal Mn, and use intermittent Type reactor, control the ion concentration of doped metal Mn at 2000ppm, the temperature at 60°C, the flow rate of protective gas at 5L/min, and the amount of reducing agent accounted for 0.06% of the solution.
  • the pH values are respectively controlled at 10.5-11 and 9.5-10, and wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 10 and a concentration of 12.5% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1025°C, a lithium-cobalt ratio of 1.05, and a holding time of 15 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 45 minutes; The heating rate per minute was raised to 1025°C and kept for 15 hours. During the sintering process, air was continuously introduced, and the air flow rate was controlled at 7.5L/min. Then the sintered product was cooled to room temperature, and then the sintered product was coarsely pulverized with a mortar.
  • the pulverized sintered product is poured into a universal pulverizer for fine crushing, and the finely pulverized sintered product is poured into a 200-mesh screen for sieving treatment to obtain small particle size doped lithium cobaltate with a particle size of 6-7 ⁇ m, Large particle size doped lithium cobalt oxide with a particle size of 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 7:3 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • cobalt sulfate solution with a concentration of 200g/L as the cobalt source, sodium hydroxide as the precipitant, EDTA solution as the complexing agent, argon as the protective gas, and ascorbic acid as the reducing agent, mix the compound doped with metal Mn, and use the batch method
  • the ion concentration of doped metal Mn is controlled at 5000ppm
  • the temperature is at 70°C
  • the flow rate of the protective gas is at 5L/min
  • the amount of reducing agent accounts for 0.1% of the solution.
  • the pH value is controlled at 10.5-11 and 9.5-10, and the wet synthesis is carried out to obtain small particle size doped cobaltous hydroxide and large particle size doped cobaltous hydroxide respectively.
  • the hydrogen peroxide solution with a pH value of 11 and a concentration of 15% was used to oxidize the small particle size doped cobaltous hydroxide and the large particle size doped cobaltous hydroxide respectively to obtain small particle size doped cobaltous hydroxide respectively.
  • the small particle size doped cobalt oxyhydroxide and the large particle size doped cobalt oxyhydroxide were washed and dried respectively, and calcined at a controlled temperature of 1050°C, a lithium-cobalt ratio of 1.1, and a holding time of 20 hours to obtain particle sizes of Doped cobalt tetroxide with a small particle size of 3-5 ⁇ m, large-sized cobalt tetroxide doped with a particle size of 10-15 ⁇ m, the tap density of the doped cobalt tetroxide is greater than 2.0g/cm 3 , and the specific surface area is 3.0-5.0m 2 /g,
  • the shape is spherical or spherical.
  • the small particle size doped tricobalt tetroxide and the large particle size doped tricobalt tetroxide were mixed with battery grade lithium carbonate in a high-speed mixer for 60 minutes; The heating rate per minute is raised to 1050°C and kept for 20 hours. During the sintering process, air is continuously introduced, and the air flow rate is controlled at 10L/min; then the sintered product is cooled to room temperature, and the sintered product is coarsely pulverized with a mortar.
  • the sintered product is poured into a universal pulverizer for fine crushing, and the finely crushed sintered product is poured into a 200-mesh screen for sieving treatment to obtain small particle size doped lithium cobaltate with a particle size of 6-7 ⁇ m, particle size Large particle size doped lithium cobalt oxide in 12-18 ⁇ m.
  • the large particle size doped lithium cobalt oxide and the small particle size doped lithium cobalt oxide are mixed according to a mass ratio of 8:2 to obtain a high voltage lithium cobalt oxide positive electrode material.
  • doped tricobalt tetroxide with controllable particle size doped with one or more elements in Al, Ni, Mg, and Mn is obtained by wet synthesis, oxidation, and calcination, and the small particle size doped type Cobalt tetroxide and large-size doped cobalt tetroxide are mixed with battery-grade lithium carbonate respectively, sintered, cooled, crushed, and sieved to realize wet doping of the precursor, so that the doping elements are evenly distributed at the atomic level, and particle sizes of 6 -7 ⁇ m, 12-18 ⁇ m doped lithium cobalt oxide, with high purity and no impurity phase, which solves the technical problem of uneven doping of the existing LiCoO 2 solid phase.
  • the prepared small particle size doped lithium cobalt oxide and large particle size doped lithium cobalt oxide are mixed according to the set mass ratio, which greatly improves the compaction density and processing performance of the high voltage lithium cobalt oxide cathode material, and effectively improves the The structural stability of the material improves the cycle performance and rate performance of the battery.

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Abstract

本发明涉及高电压钴酸锂正极材料制备技术领域，提供一种高电压钴酸锂正极材料的制备方法，包括：含钴溶液混合掺杂金属M的化合物，在间歇式反应釜，控制pH值，湿法合成小、大粒度掺杂型氢氧化亚钴，经双氧水溶液氧化，得小、大粒度掺杂型羟基氧化钴；洗涤、干燥、煅烧小、大粒度掺杂型羟基氧化钴，得小、大粒度掺杂型四氧化三钴；将小、大粒度掺杂型四氧化三钴分别与电池级碳酸锂混合，烧结、冷却、粉碎、过筛，得小、大粒度掺杂型钴酸锂；将大、小粒度掺杂型钴酸锂按设定质量比混合，得高电压钴酸锂正极材料。本发明能够使钴酸锂固相掺杂均匀，提高高电压钴酸锂正极材料的压实密度、加工性能与结构稳定性，提升电池的循环性能与倍率性能。

Description

一种高电压钴酸锂正极材料的制备方法 技术领域
本发明涉及高电压钴酸锂正极材料制备技术领域，尤其是涉及一种高电压钴酸锂正极材料的制备方法。
背景技术
钴酸锂正极材料具有比容量大、能量密度高、工作电压平台高、循环性能好、寿命长等特点，主要应用于3C数码领域。随着数码产品的更新换代，钴酸锂正朝着高电压、高压实、快速充放电的方向发展。
目前LiCoO 2正极材料的研发主要集中于开发具有更高充电电压、更高能量密度、更长循环寿命和可接受的低成本与安全水平的产品。提高充电截止电压，可以最大限度地发挥钴酸锂的容量，但材料充放电，LiCoO 2晶格结构就会坍塌，循环稳定性和倍率性能会降低。
锂离子电池正极材料的微观结构和宏观性能受合成方法的影响较为明显，不同的合成方法下材料的形貌、结构和电化学性能等方面存在很大的差异。目前LiCoO 2正极材料合成中应用最广泛的合成方法有高温固相法、湿化学法和喷雾干燥法等。
高温固相法合成LiCoO 2通常是以锂和钴的碳酸盐、硝酸盐、乙酸盐、氧化物或者氢氧化物为原料，充分混合后再在空气气氛下于900～1050℃煅烧。高温固相反应过程中原子或离子穿过各物相之间的界面，并通过各物相区，形成原子或离子的交互扩散。整个反应的推动力是反应物和生成物之间自由能之差，影响反应速率的重要因素是：(1)反应固体颗粒之间的接触面积及表面积；(2)产物相的成核速率；(3)原子或离子通过各物相特别是通过产物相的扩散速率。高温固相法工艺简单且易于控制，适用于工业化生产，但也存在受原料限制大、能耗高和反应时间长等缺点。
湿化学法是共沉淀法、溶胶凝胶法以及水热法等一系列材料合成方法的统称；与高温固相法相比，该类方法合成材料的反应属于原子或者分子级别，可以有效控制产物的形貌、组成成分和微观结构，合成的材料具有结晶程度高、粒度大小均匀以及比表面积大等特点。在合成工艺上，由该类方法制得的前驱体一次粒度细小，物料混合均匀，因而热处理温度可以降低，时间也可以缩短，大大降低了能耗。
喷雾干燥法是目前合成球形材料最有效和常用的方法，其流程可以描述如下：将原料配制成溶液或者浆料，经雾化器雾化分散成均匀的雾滴，由气流带入具有一定温度的空腔内， 快速完成溶剂蒸发、溶质成核、干燥、热分解等一系列物理化学反应，最后烧结制成所需的材料。该方法能够在短时间内实现热量和质量的传递，避免了混和、干燥、再破碎的繁琐工艺流程，合成的材料球形度好，粒度大小可控且分布均匀，有利于提高材料的振实密度。
掺杂主要是用各种不同的元素取代材料组分中部分元素以形成均相固溶体的一种改性手段，旨在稳定材料的结构，从而相应提高其电化学性能和热稳定性，但有时会牺牲部分容量。固相掺杂的优势是简单方便，缺点是不均匀。
发明内容
针对现有技术存在的问题，本发明提供一种高电压钴酸锂正极材料的制备方法，能够使得LiCoO 2固相掺杂均匀，提高高电压钴酸锂正极材料的压实密度与加工性能，有效改善材料的结构稳定性，提升电池的循环性能与倍率性能。
本发明的技术方案为：
一种高电压钴酸锂正极材料的制备方法，其特征在于，包括下述步骤：
步骤1：制备掺杂型四氧化三钴
步骤1.1：制备掺杂型氢氧化亚钴
以含钴溶液为钴源、氢氧化钠为沉淀剂、氨水或EDTA溶液为络合剂、氮气或氩气为保护气体、水合肼溶液或抗坏血酸为还原剂，混合掺杂金属M的化合物，利用间歇式反应釜，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，得到的掺杂型氢氧化亚钴分别记为小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴；
步骤1.2：制备羟基氧化钴
湿法合成结束后，利用双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，得到的掺杂型羟基氧化钴分别记为小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴；
步骤1.3：制备掺杂型四氧化三钴
分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥、煅烧，得到的掺杂型四氧化三钴(Co 1-xM x) 3O 4分别为粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴；
步骤2：制备掺杂型钴酸锂
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂混合，烧结、冷却、粉碎、过筛，得到的掺杂型钴酸锂LiCo 1-xM xO 2分别记为小粒度掺杂型钴酸锂、大粒度掺杂型钴酸锂；其中，x≤0.005；
步骤3：将所述大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照设定的质量比进行混合， 得到高电压钴酸锂正极材料。
进一步的，所述步骤1.1中，所述掺杂金属M为Al、Ni、Mg、Mn中的一种或多种。
进一步的，所述步骤1.1中，所述掺杂金属M的离子浓度控制在500-5000ppm。
进一步的，所述步骤1.1中，所述含钴溶液为硝酸钴、氯化钴、硫酸钴、草酸钴溶液中的一种或几种，所述含钴溶液的浓度为80-200g/L，湿法合成过程中的温度控制在50-70℃、保护气体的流量控制在5L/min、还原剂的使用量占溶液的0.02％-0.1％。
进一步的，所述步骤1.2中，控制pH值在9.5-11，双氧水溶液的浓度为10％-15％。
进一步的，所述步骤1.3中，煅烧过程的温度控制在1000-1050℃、锂钴比控制在1.0-1.1、保温时间控制在10-20h。
进一步的，步骤1.3中，所述掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
进一步的，步骤2中，所述混合包括：将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合30-60min；
所述烧结包括：将混合物置于匣钵中，随后放入马弗炉中，以5-10℃/min的升温速率升温至1000-1050℃并保温10-20h，烧结过程中连续通入空气，空气的流量控制在5-10L/min；
所述冷却包括：将烧结品冷却至室温；
所述粉碎包括：用研钵粗粉碎烧结品，随后将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎；
所述过筛包括：将粉碎后的烧结品倒入200目的筛网中进行过筛处理。
进一步的，所述步骤3中，设定的质量比为(5:5)-(8:2)。
进一步的，所述步骤3中，设定的质量比为7:3或8:2。
本发明的有益效果为：
(1)本发明通过湿法合成、氧化、煅烧得到掺杂Al、Ni、Mg、Mn中一种或多种元素的粒度可控的掺杂型四氧化三钴，并将小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂混合、烧结、冷却、粉碎、过筛，实现前驱体湿法掺杂，使得掺杂元素在原子级别上分布均匀，能够得到粒度分别为6-7μm、12-18μm的掺杂型钴酸锂，纯度高、无杂相，解决了现有LiCoO 2固相掺杂不均匀的技术问题。
(2)本发明将制备的小粒度掺杂型钴酸锂与大粒度掺杂型钴酸锂按照设定的质量比进行混合，大大提高了高电压钴酸锂正极材料的压实密度与加工性能，有效改善了材料的结构稳 定性，提升了电池的循环性能与倍率性能。
(3)本发明通过掺杂Al、Mn能够稳定结构，且降低生产成本；掺杂Mg能够提高材料的离子导电性，有利于提升钴酸锂正极材料的倍率性能；掺杂Ni能够在提高钴酸锂正极材料的容量的同时不影响倍率性能，而且Ni的价格低，能够降低生产成本
(4)本发明工艺简单、易于操作，有利于大规模工业化生产。
附图说明
图1为本发明的高电压钴酸锂正极材料的制备方法的流程图。
具体实施方式
下面将结合附图和具体实施方式，对本发明作进一步描述。
如图1所示，本发明的高电压钴酸锂正极材料的制备方法，包括下述步骤：
步骤1：制备掺杂型四氧化三钴
步骤1.1：制备掺杂型氢氧化亚钴
以含钴溶液为钴源、氢氧化钠为沉淀剂、氨水或EDTA溶液为络合剂、氮气或氩气为保护气体、水合肼溶液或抗坏血酸为还原剂，混合掺杂金属M的化合物，利用间歇式反应釜，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，得到的掺杂型氢氧化亚钴分别记为小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。
本发明中，掺杂金属M为Al、Ni、Mg、Mn中的一种或多种。其中，掺杂Al、Mn能够稳定结构，且降低生产成本；Mg的半径与Co接近，掺杂Mg能够提高材料的离子导电性，有利于提升钴酸锂正极材料的倍率性能；掺杂Ni能够在提高钴酸锂正极材料的容量的同时不影响倍率性能，而且Ni的价格低，能够降低生产成本。
掺杂金属M的离子浓度控制在500-5000ppm。所述含钴溶液为硝酸钴、氯化钴、硫酸钴、草酸钴溶液中的一种或几种，所述含钴溶液的浓度为80-200g/L，湿法合成过程中的温度控制在50-70℃、保护气体的流量控制在5L/min、还原剂的使用量占溶液的0.02％-0.1％。
步骤1.2：制备羟基氧化钴
湿法合成结束后，利用双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，得到的掺杂型羟基氧化钴分别记为小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。
氧化过程中，控制pH值在9.5-11，双氧水溶液的浓度为10％-15％。
步骤1.3：制备掺杂型四氧化三钴
分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥、煅烧，得到的掺杂型四氧化三钴(Co 1-xM x) 3O 4分别为粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴。
煅烧过程中，温度控制在1000-1050℃、锂钴比控制在1.0-1.1、保温时间控制在10-20h。
步骤1.3中得到的掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
步骤2：制备掺杂型钴酸锂
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂混合，烧结、冷却、粉碎、过筛，得到的掺杂型钴酸锂LiCo 1-xM xO 2分别记为小粒度掺杂型钴酸锂、大粒度掺杂型钴酸锂；其中，x≤0.005。
本发明中，所述混合包括：将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合30-60min；
所述烧结包括：将混合物置于匣钵中，随后放入马弗炉中，以5-10℃/min的升温速率升温至1000-1050℃并保温10-20h，烧结过程中连续通入空气，空气的流量控制在5-10L/min；
所述冷却包括：将烧结品冷却至室温；
所述粉碎包括：用研钵粗粉碎烧结品，随后将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎；
所述过筛包括：将粉碎后的烧结品倒入200目的筛网中进行过筛处理。
步骤3：将所述大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照设定的质量比进行混合，得到高电压钴酸锂正极材料。
本发明中设定的质量比为(5:5)-(8:2)。优选的，设定的质量比为7:3或8:2。
实施例1
以浓度为80g/L的硝酸钴溶液为钴源、氢氧化钠为沉淀剂、氨水溶液为络合剂、氮气为保护气体、水合肼溶液为还原剂，混合掺杂金属Al的化合物，利用间歇式反应釜，控制掺杂金属Al的离子浓度在500ppm、温度在50℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.02％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为9.5、浓度为10％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化 钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1000℃、锂钴比在1.0、保温时间在10h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合30min；将混合物置于匣钵中，随后放入马弗炉中，以5℃/min的升温速率升温至1000℃并保温10h，烧结过程中连续通入空气，空气的流量控制在5L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照5:5的质量比进行混合，得到高电压钴酸锂正极材料。
实施例2
以浓度为140g/L的氯化钴溶液为钴源、氢氧化钠为沉淀剂、EDTA溶液为络合剂、氩气为保护气体、抗坏血酸为还原剂，混合掺杂金属Al的化合物，利用间歇式反应釜，控制掺杂金属Al的离子浓度在2000ppm、温度在60℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.06％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为10、浓度为12.5％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1025℃、锂钴比在1.05、保温时间在15h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合45min；将混合物置于匣钵中，随后放入马弗炉中，以7.5℃/min的升温速率升温至1025℃并保温15h，烧结过程中连续通入空气，空气的流量控制在7.5L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺 杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照7:3的质量比进行混合，得到高电压钴酸锂正极材料。
实施例3
以浓度为200g/L的硫酸钴溶液为钴源、氢氧化钠为沉淀剂、EDTA溶液为络合剂、氩气为保护气体、抗坏血酸为还原剂，混合掺杂金属Al的化合物，利用间歇式反应釜，控制掺杂金属Al的离子浓度在5000ppm、温度在70℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.1％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为11、浓度为15％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1050℃、锂钴比在1.1、保温时间在20h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合60min；将混合物置于匣钵中，随后放入马弗炉中，以10℃/min的升温速率升温至1050℃并保温20h，烧结过程中连续通入空气，空气的流量控制在10L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照8:2的质量比进行混合，得到高电压钴酸锂正极材料。
实施例4
以浓度为80g/L的硝酸钴溶液为钴源、氢氧化钠为沉淀剂、氨水溶液为络合剂、氮气为保护气体、水合肼溶液为还原剂，混合掺杂金属Ni的化合物，利用间歇式反应釜，控制掺杂金属Ni的离子浓度在500ppm、温度在50℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.02％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束 后，利用pH值为9.5、浓度为10％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1000℃、锂钴比在1.0、保温时间在10h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合30min；将混合物置于匣钵中，随后放入马弗炉中，以5℃/min的升温速率升温至1000℃并保温10h，烧结过程中连续通入空气，空气的流量控制在5L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照5:5的质量比进行混合，得到高电压钴酸锂正极材料。
实施例5
以浓度为140g/L的氯化钴溶液为钴源、氢氧化钠为沉淀剂、EDTA溶液为络合剂、氩气为保护气体、抗坏血酸为还原剂，混合掺杂金属Ni的化合物，利用间歇式反应釜，控制掺杂金属Ni的离子浓度在2000ppm、温度在60℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.06％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为10、浓度为12.5％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1025℃、锂钴比在1.05、保温时间在15h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合45min；将混合物置于匣钵中，随后放入马弗炉中，以7.5℃/min的升温速率升温至1025℃并保温15h，烧结过程中连续通入空气，空气的流量控制在7.5L/min；随后将烧 结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照7:3的质量比进行混合，得到高电压钴酸锂正极材料。
实施例6
以浓度为200g/L的硫酸钴溶液为钴源、氢氧化钠为沉淀剂、EDTA溶液为络合剂、氩气为保护气体、抗坏血酸为还原剂，混合掺杂金属Ni的化合物，利用间歇式反应釜，控制掺杂金属Ni的离子浓度在5000ppm、温度在70℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.1％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为11、浓度为15％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1050℃、锂钴比在1.1、保温时间在20h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合60min；将混合物置于匣钵中，随后放入马弗炉中，以10℃/min的升温速率升温至1050℃并保温20h，烧结过程中连续通入空气，空气的流量控制在10L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照8:2的质量比进行混合，得到高电压钴酸锂正极材料。
实施例7
以浓度为80g/L的硝酸钴溶液为钴源、氢氧化钠为沉淀剂、氨水溶液为络合剂、氮气为保护气体、水合肼溶液为还原剂，混合掺杂金属Mg的化合物，利用间歇式反应釜，控制掺杂金属Mg的离子浓度在500ppm、温度在50℃、保护气体的流量在5L/min、还原剂的使用 量占溶液的0.02％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为9.5、浓度为10％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1000℃、锂钴比在1.0、保温时间在10h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合30min；将混合物置于匣钵中，随后放入马弗炉中，以5℃/min的升温速率升温至1000℃并保温10h，烧结过程中连续通入空气，空气的流量控制在5L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照5:5的质量比进行混合，得到高电压钴酸锂正极材料。
实施例8
以浓度为140g/L的氯化钴溶液为钴源、氢氧化钠为沉淀剂、EDTA溶液为络合剂、氩气为保护气体、抗坏血酸为还原剂，混合掺杂金属Mg的化合物，利用间歇式反应釜，控制掺杂金属Mg的离子浓度在2000ppm、温度在60℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.06％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为10、浓度为12.5％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1025℃、锂钴比在1.05、保温时间在15h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速 混料机中混合45min；将混合物置于匣钵中，随后放入马弗炉中，以7.5℃/min的升温速率升温至1025℃并保温15h，烧结过程中连续通入空气，空气的流量控制在7.5L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照7:3的质量比进行混合，得到高电压钴酸锂正极材料。
实施例9
以浓度为200g/L的硫酸钴溶液为钴源、氢氧化钠为沉淀剂、EDTA溶液为络合剂、氩气为保护气体、抗坏血酸为还原剂，混合掺杂金属Mg的化合物，利用间歇式反应釜，控制掺杂金属Mg的离子浓度在5000ppm、温度在70℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.1％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为11、浓度为15％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1050℃、锂钴比在1.1、保温时间在20h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合60min；将混合物置于匣钵中，随后放入马弗炉中，以10℃/min的升温速率升温至1050℃并保温20h，烧结过程中连续通入空气，空气的流量控制在10L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照8:2的质量比进行混合，得到高电压钴酸锂正极材料。
实施例10
以浓度为80g/L的硝酸钴溶液为钴源、氢氧化钠为沉淀剂、氨水溶液为络合剂、氮气为 保护气体、水合肼溶液为还原剂，混合掺杂金属Mn的化合物，利用间歇式反应釜，控制掺杂金属Mn的离子浓度在500ppm、温度在50℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.02％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为9.5、浓度为10％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1000℃、锂钴比在1.0、保温时间在10h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合30min；将混合物置于匣钵中，随后放入马弗炉中，以5℃/min的升温速率升温至1000℃并保温10h，烧结过程中连续通入空气，空气的流量控制在5L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照5:5的质量比进行混合，得到高电压钴酸锂正极材料。
实施例11
以浓度为140g/L的氯化钴溶液为钴源、氢氧化钠为沉淀剂、EDTA溶液为络合剂、氩气为保护气体、抗坏血酸为还原剂，混合掺杂金属Mn的化合物，利用间歇式反应釜，控制掺杂金属Mn的离子浓度在2000ppm、温度在60℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.06％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为10、浓度为12.5％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1025℃、锂钴比在1.05、保温时间在15h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴 的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合45min；将混合物置于匣钵中，随后放入马弗炉中，以7.5℃/min的升温速率升温至1025℃并保温15h，烧结过程中连续通入空气，空气的流量控制在7.5L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照7:3的质量比进行混合，得到高电压钴酸锂正极材料。
实施例12
以浓度为200g/L的硫酸钴溶液为钴源、氢氧化钠为沉淀剂、EDTA溶液为络合剂、氩气为保护气体、抗坏血酸为还原剂，混合掺杂金属Mn的化合物，利用间歇式反应釜，控制掺杂金属Mn的离子浓度在5000ppm、温度在70℃、保护气体的流量在5L/min、还原剂的使用量占溶液的0.1％，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，分别得到小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴。湿法合成结束后，利用pH值为11、浓度为15％的双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，分别得到小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴。分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥，并控制温度在1050℃、锂钴比在1.1、保温时间在20h进行煅烧，分别得到粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴，掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合60min；将混合物置于匣钵中，随后放入马弗炉中，以10℃/min的升温速率升温至1050℃并保温20h，烧结过程中连续通入空气，空气的流量控制在10L/min；随后将烧结品冷却至室温，再用研钵粗粉碎烧结品，将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎，将精粉碎后的烧结品倒入200目的筛网中进行过筛处理，分别得到粒度在6-7μm的小粒度掺杂型钴酸锂、粒度在12-18μm的大粒度掺杂型钴酸锂。
将大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照8:2的质量比进行混合，得到高电压钴酸锂正极材料。
本发明的上述实施例中，通过湿法合成、氧化、煅烧得到掺杂Al、Ni、Mg、Mn中一种或多种元素的粒度可控的掺杂型四氧化三钴，并将小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂混合、烧结、冷却、粉碎、过筛，实现前驱体湿法掺杂，使得掺杂元素在原子级别上分布均匀，能够得到粒度分别为6-7μm、12-18μm的掺杂型钴酸锂，纯度高、无杂相，解决了现有LiCoO 2固相掺杂不均匀的技术问题。将制备的小粒度掺杂型钴酸锂与大粒度掺杂型钴酸锂按照设定的质量比进行混合，大大提高了高电压钴酸锂正极材料的压实密度与加工性能，有效改善了材料的结构稳定性，提升了电池的循环性能与倍率性能。
显然，上述实施例仅仅是本发明的一部分实施例，而不是全部的实施例。上述实施例仅用于解释本发明，并不构成对本发明保护范围的限定。基于上述实施例，本领域技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，也即凡在本申请的精神和原理之内所作的所有修改、等同替换和改进等，均落在本发明要求的保护范围内。

Claims (10)

  1. 一种高电压钴酸锂正极材料的制备方法，其特征在于，包括下述步骤：
    步骤1：制备掺杂型四氧化三钴
    步骤1.1：制备掺杂型氢氧化亚钴
    以含钴溶液为钴源、氢氧化钠为沉淀剂、氨水或EDTA溶液为络合剂、氮气或氩气为保护气体、水合肼溶液或抗坏血酸为还原剂，混合掺杂金属M的化合物，利用间歇式反应釜，通过控制合成初期晶核生成数量方式，分别控制pH值在10.5-11、9.5-10，进行湿法合成，得到的掺杂型氢氧化亚钴分别记为小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴；
    步骤1.2：制备羟基氧化钴
    湿法合成结束后，利用双氧水溶液分别对所述小粒度掺杂型氢氧化亚钴、大粒度掺杂型氢氧化亚钴进行氧化，得到的掺杂型羟基氧化钴分别记为小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴；
    步骤1.3：制备掺杂型四氧化三钴
    分别对所述小粒度掺杂型羟基氧化钴、大粒度掺杂型羟基氧化钴进行洗涤、干燥、煅烧，得到的掺杂型四氧化三钴(Co 1-xM x) 3O 4分别为粒度在3-5μm的小粒度掺杂型四氧化三钴、粒度在10-15μm的大粒度掺杂型四氧化三钴；
    步骤2：制备掺杂型钴酸锂
    将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂混合，烧结、冷却、粉碎、过筛，得到的掺杂型钴酸锂LiCo 1-xM xO 2分别记为小粒度掺杂型钴酸锂、大粒度掺杂型钴酸锂；其中，x≤0.005；
    步骤3：将所述大粒度掺杂型钴酸锂与小粒度掺杂型钴酸锂按照设定的质量比进行混合，得到高电压钴酸锂正极材料。
  2. 根据权利要求1所述的高电压钴酸锂正极材料的制备方法，其特征在于，所述步骤1.1中，所述掺杂金属M为Al、Ni、Mg、Mn中的一种或多种。
  3. 根据权利要求1所述的高电压钴酸锂正极材料的制备方法，其特征在于，所述步骤1.1中，所述掺杂金属M的离子浓度控制在500-5000ppm。
  4. 根据权利要求1所述的高电压钴酸锂正极材料的制备方法，其特征在于，所述步骤1.1中，所述含钴溶液为硝酸钴、氯化钴、硫酸钴、草酸钴溶液中的一种或几种，所述含钴溶液的浓度为80-200g/L，湿法合成过程中的温度控制在50-70℃、保护气体的流量控制在5L/min、还原剂的使用量占溶液的0.02％-0.1％。
  5. 根据权利要求1所述的高电压钴酸锂正极材料的制备方法，其特征在于，所述步骤1.2中，控制pH值在9.5-11，双氧水溶液的浓度为10％-15％。
  6. 根据权利要求1所述的高电压钴酸锂正极材料的制备方法，其特征在于，所述步骤1.3中，煅烧过程的温度控制在1000-1050℃、锂钴比控制在1.0-1.1、保温时间控制在10-20h。
  7. 根据权利要求1所述的高电压钴酸锂正极材料的制备方法，其特征在于，步骤1.3中，所述掺杂型四氧化三钴的振实密度大于2.0g/cm 3、比表面积为3.0-5.0m 2/g、形状为球形或类球形。
  8. 根据权利要求1所述的高电压钴酸锂正极材料的制备方法，其特征在于，步骤2中，所述混合包括：将所述小粒度掺杂型四氧化三钴、大粒度掺杂型四氧化三钴分别与电池级碳酸锂在高速混料机中混合30-60min；
    所述烧结包括：将混合物置于匣钵中，随后放入马弗炉中，以5-10℃/min的升温速率升温至1000-1050℃并保温10-20h，烧结过程中连续通入空气，空气的流量控制在5-10L/min；
    所述冷却包括：将烧结品冷却至室温；
    所述粉碎包括：用研钵粗粉碎烧结品，随后将粗粉碎的烧结品倒入万能粉碎机中进行精粉碎；
    所述过筛包括：将粉碎后的烧结品倒入200目的筛网中进行过筛处理。
  9. 根据权利要求1所述的高电压钴酸锂正极材料的制备方法，其特征在于，所述步骤3中，设定的质量比为(5:5)-(8:2)。
  10. 根据权利要求9所述的高电压钴酸锂正极材料的制备方法，其特征在于，所述步骤3中，设定的质量比为7:3或8:2。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101667663A (zh) * 2007-10-10 2010-03-10 日立麦克赛尔株式会社 非水二次电池及使用其的设备
CN102709519A (zh) * 2006-10-26 2012-10-03 日立麦克赛尔能源株式会社 非水二次电池
JP2012252806A (ja) * 2011-05-31 2012-12-20 Sanyo Electric Co Ltd 非水電解質二次電池
CN108298596A (zh) * 2018-04-03 2018-07-20 兰州金川新材料科技股份有限公司 一种大粒度掺杂四氧化三钴的制备方法
CN114204008A (zh) * 2021-11-23 2022-03-18 格林美（江苏）钴业股份有限公司 一种高电压钴酸锂正极材料的制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105329954B (zh) * 2014-08-11 2017-09-19 荆门市格林美新材料有限公司 大粒径氢氧化钴及其制备方法
JP6582824B2 (ja) * 2015-09-30 2019-10-02 住友金属鉱山株式会社 ニッケルマンガン含有複合水酸化物およびその製造方法
CN105514411B (zh) * 2015-12-19 2018-08-10 山东玉皇新能源科技有限公司 一种锂离子电池正极材料的合成方法
CN108455686B (zh) * 2018-05-21 2020-11-06 兰州金川新材料科技股份有限公司 一种掺铌钨钽四氧化三钴的制备方法
CN108807881A (zh) * 2018-05-21 2018-11-13 兰州金川新材料科技股份有限公司 一种体相掺铝四氧化三钴的制备方法
CN108682850B (zh) * 2018-05-28 2021-04-06 格林美（江苏）钴业股份有限公司 一种微富锂高能量密度钴酸锂正极材料及其制备方法
CN112850802A (zh) * 2019-11-28 2021-05-28 荆门市格林美新材料有限公司 一种宽分布四氧化三钴的生产工艺及生产装置
CN112537802B (zh) * 2020-12-08 2022-11-22 衢州华友钴新材料有限公司 一种高电压锂电池前驱体掺杂氢氧化钴的制备方法
CN113511690B (zh) * 2021-07-16 2023-03-24 北京泰丰先行新能源科技有限公司 均匀掺铝的大小颗粒四氧化三钴的制备方法及正极材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102709519A (zh) * 2006-10-26 2012-10-03 日立麦克赛尔能源株式会社 非水二次电池
CN101667663A (zh) * 2007-10-10 2010-03-10 日立麦克赛尔株式会社 非水二次电池及使用其的设备
JP2012252806A (ja) * 2011-05-31 2012-12-20 Sanyo Electric Co Ltd 非水電解質二次電池
CN108298596A (zh) * 2018-04-03 2018-07-20 兰州金川新材料科技股份有限公司 一种大粒度掺杂四氧化三钴的制备方法
CN114204008A (zh) * 2021-11-23 2022-03-18 格林美（江苏）钴业股份有限公司 一种高电压钴酸锂正极材料的制备方法

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