CN109585843B - Preparation method of high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor - Google Patents

Preparation method of high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor Download PDF

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CN109585843B
CN109585843B CN201811336793.9A CN201811336793A CN109585843B CN 109585843 B CN109585843 B CN 109585843B CN 201811336793 A CN201811336793 A CN 201811336793A CN 109585843 B CN109585843 B CN 109585843B
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nickel
cobalt
aluminum
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CN109585843A (en
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姚耀春
王韵珂
李代国
姜国强
杨斌
马文会
戴永年
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Kunming University of Science and Technology
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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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • H01M4/36—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

Abstract

The invention discloses a preparation method of a high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor, which comprises the steps of mixing cleaned nickel particles with N, N-dimethylformamide and ethylenediamine, and obtaining high-nickel ternary positive electrode material Ni according to the obtained high-nickel ternary positive electrode material1‑y‑xCoyAlxAdding cobalt salt according to the stoichiometric ratio, stirring and uniformly mixing, reacting at constant temperature, cooling, taking out a product, repeatedly cleaning with deionized water and ethanol, and drying in vacuum; mixing the product with ethylene glycol and anhydrous ethylenediamine, adding aluminum salt according to a stoichiometric ratio, reacting at a constant temperature, naturally cooling to room temperature after the reaction is finished, taking out the product, cleaning, and drying in vacuum to obtain high-nickel ternary nickel cobalt aluminum positive electrode material precursor powder Ni1‑y‑xCoyAlx(ii) a The nickel-cobalt-aluminum compound precursor prepared by the method is regular spherical, has good sphericity, uniform granularity and high tap density, is suitable for being used as a precursor for industrially producing the lithium ion battery anode material, and has the advantages of simple process, high controllability, high yield, high purity, production cost saving and environmental protection.

Description

Preparation method of high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a preparation method of a high-nickel ternary nickel-cobalt-aluminum anode material precursor.
Background
In order to meet the increasing requirements of people on battery capacity, energy density and rate capability, the high nickel material becomes one of the development directions leading to the future lithium ion battery anode material. LiNixCoyAl1-x-yO2The anode material integrates LiNiO2And LiCoO2The advantages of the material.Co and A1 Co-doping has a firm effect on the material structure, inhibits cation mixed discharge, greatly improves the cycle stability and safety performance, has the advantages of high capacity, high energy density and good rate capability, and can meet the requirement of a power battery on the anode material. The 18650 type battery used for Tesla Model-S electric vehicle has positive electrode material LiNi0.8Co0.15Al0.05O2Abbreviated NCA, japan also applies this material to the pluris plug-in hybrid vehicles.
All physical and chemical properties and electrochemical properties of the cathode material are related to macroscopic physical and chemical properties and microscopic morphological structures of the precursor material. Therefore, the method for improving the ordering of the crystal structure of the precursor material and optimizing the primary grain morphology and the secondary grain morphology has the following advantages of improving the physicochemical and electrochemical properties of the ternary cathode material: tap density, cycling stability, rate discharge performance and the like all have important influences.
In patent CN201310096403, an aqueous solution of nickel sulfate, cobalt salt and aluminum salt, an ammonia solution (as a complexing agent), a sodium hydroxide solution (as a precipitant) and a hydrazine hydrate solution (as an antioxidant) are continuously injected into a reaction kettle through a precise flow control system to obtain a nickel-cobalt-aluminum precursor, but due to ni (oh)2(s) and Co (OH)2K of(s)spIs 10-14.7And 10-14.8And Al (OH)3K of(s)spIs 10-33，Al(OH)3(s) precipitation rate much greater than that of Ni (OH)2(s) and Co (OH)2(s) causes failure in uniform coprecipitation of three metal elements of Ni, Co and Al, and due to Al (OH)3The rapid precipitation of(s) can generate a large number of fine crystal nuclei, which leads to the fact that crystals cannot grow up and the required precursors of micron-sized particles cannot be obtained. Patents CN201610014278 and CN201511023197 first prepare a co-precipitated hydroxide of nickel and cobalt, and then mix with an aluminum-containing compound to sinter to obtain the nickel-cobalt-aluminum oxide. The method has the advantages of complicated steps, increased cost and low tap density of the finally-fired nickel-cobalt-aluminum oxide; in the methods, ammonia water is used as a complexing agent, the ammonia water is easy to decompose to release ammonia gas, the decomposition speed is higher when the temperature is higher,an explosive atmosphere can be formed; the ammonia nitrogen compound formed by the ammonia water causes pollution to the environment and certain damage to the research personnel.
Disclosure of Invention
In view of various technical problems, the invention provides the preparation method of the high-nickel ternary nickel cobalt aluminum positive electrode material precursor with high tap density, good sphericity and uniform element distribution.
A preparation method of a high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor specifically comprises the following steps:
(1) putting the cleaned nickel particles, N-Dimethylformamide (DMF) and Ethylenediamine (EDA) into a polytetrafluoroethylene high-pressure reaction kettle for mixing, and finally obtaining the high-nickel ternary nickel cobalt aluminum cathode material Ni1-y-xCoyAlxAdding cobalt salt according to the stoichiometric ratio, stirring and uniformly mixing, wherein y is more than 0 and less than or equal to 0.15, x is more than 0 and less than or equal to 0.05, putting the reaction kettle into an oven for constant-temperature reaction, naturally cooling to room temperature after the reaction is finished, taking out a product, repeatedly cleaning with deionized water and ethanol, and then carrying out vacuum drying in a vacuum drying oven;
(2) mixing the product of step (1) with ethylene glycol and Ethylenediamine (EDA), and adding Ni1-y-xCoyAlxAdding aluminum salt into the mixture according to the stoichiometric ratio, placing the mixture into an oven for constant-temperature reaction, introducing aluminum ions by a cation replacement method, naturally cooling to room temperature after the reaction is finished, taking out the product, repeatedly cleaning the product with deionized water and ethanol, and then performing vacuum drying in a vacuum drying oven to obtain spherical high-nickel ternary nickel cobalt aluminum cathode material precursor powder Ni with uniform granularity, high mechanical strength, good conductivity and high porosity1-y-xCoyAlx。
The nickel particles in the step (1) are particles with the particle size of 5-25 mu m after the nickel screen is crushed, small particles are beneficial to the replacement reaction of ions in the solution, the nickel particle cleaning is ultrasonic cleaning by adopting a mixed solution of alcohol and deionized water, the cleaning frequency is not less than 6 times, each time lasts for 10-15 minutes, and the proportion of the alcohol to the deionized water in the mixed solution is 1: 1.
And (2) mixing the nickel particles, N-Dimethylformamide (DMF) and Ethylenediamine (EDA) according to the molar ratio of nickel to N, N-Dimethylformamide (DMF) to Ethylenediamine (EDA) of 1: 100-150: 200-300.
The cobalt salt in the step (1) is one or a mixture of more of cobalt naphthenate, cobalt oxalate and cobalt acetate in any proportion.
The temperature of the constant-temperature reaction in the step (1) and the step (2) is 150-190 ℃, the time is 6-12 h, the degree of ion replacement can be effectively controlled by adjusting the replacement time, the replacement reaction is incomplete due to too short time, and ions cannot be deposited on the substrate.
And (3) drying in the vacuum in the step (1) and the step (2) at the temperature of 60-80 ℃ for 12-24 hours.
And (3) mixing the product obtained in the step (1) in the step (2) with ethylene glycol and Ethylenediamine (EDA) according to the molar ratio of cobalt to ethylene glycol to Ethylenediamine (EDA) in the product obtained in the step (1) of 1: 700-900: 350-450.
The aluminum salt in the step (2) is aluminum sulfate, aluminum nitrate, sodium metaaluminate or aluminum chloride.
The invention has the following beneficial effects:
(1) for the battery, the structure and the morphology of the electrode material are controlled to be beneficial to improving the performance, and the active material is synthesized on the nickel mesh substrate with the three-dimensional framework, so that the preparation process of the electrode is simplified, and the specific capacity of a device is increased; solve the problem of due to Ni (OH)2(s)、Co(OH)2K of(s)sp(10 each)-14.7And 10-14.8) And Al (OH)3K of(s)sp（10-33) The problem that three metal elements of Ni, Co and Al can not realize uniform coprecipitation caused by overlarge difference is solved by adopting a simple solvothermal method to synthesize the microspheres on the nickel mesh substrate, so that the nucleation rate in the crystallization process can be reduced, all the components which are uniformly mixed in the solution are precipitated together according to the stoichiometric ratio, the orderliness of the microcrystal structure of the material is effectively improved, and the stacking density of a sample is improved.
(2) The molar ratio of Ni, Co and Al elements in the nickel-cobalt-aluminum compound prepared by the invention is the same as that of the Ni, Co and Al elements in the target molecular formula, so that the problem of Al caused in the preparation of the nickel-cobalt-aluminum hydroxide precursor in the prior art is solved3+The nickel, the cobalt and the aluminum are not uniformly distributed due to incomplete precipitation.
(3) The nickel-cobalt-aluminum compound precursor prepared by the method is regular spherical, has good sphericity, uniform granularity and high tap density (2.35-2.88 g/cm)3) And is suitable for being used as a precursor for the industrial production of the lithium ion battery anode material.
(4) The nickel-cobalt-aluminum compound precursor prepared by the method is of a porous structure, so that the specific surface area of the material is increased, and the method is very beneficial to improving the electrochemical performance of the material.
(5) The invention has simple process, high controllability, high yield and high purity, saves the production cost and protects the environment.
Drawings
FIG. 1 is a scanning electron micrograph of a product prepared in example 1 of the present invention;
FIG. 2 is a graph showing the results of the initial discharge test after the battery of example 1 of the present invention is assembled;
FIG. 3 is a graph of the results of the initial discharge test after assembly of a battery according to example 2 of the present invention;
fig. 4 is a graph showing the results of the initial discharge test after the battery of example 3 of the present invention was assembled.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
A preparation method of a high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor specifically comprises the following steps:
(1) crushing a nickel screen to obtain nickel particles with the particle size of 5-10 mu m, wherein small particles are beneficial to the replacement reaction of ions in the solution, ultrasonically cleaning the nickel particles by adopting a mixed solution of alcohol and deionized water for 6 times, wherein the ratio of the alcohol to the deionized water in the mixed solution is 1:1, cleaning the cleaned nickel particles and N, N-dimethyl benzene for 15 minutes each time, and mixing the cleaned nickel particles with N, N-dimethyl benzeneMixing Dimethylformamide (DMF) and Ethylenediamine (EDA) in a polytetrafluoroethylene high-pressure reaction kettle according to the molar ratio of nickel to N, N-Dimethylformamide (DMF) to Ethylenediamine (EDA) of 1:100:200, and finally obtaining the high-nickel ternary nickel cobalt aluminum positive electrode material Ni1-y-xCoyAlxAdding cobalt salt into the mixture according to the stoichiometric ratio, and uniformly stirring and mixing, wherein y =0.1 and x =0.05, namely the molecular formula of the high-nickel ternary nickel cobalt aluminum cathode material is Ni0.85Co0.1Al0.05The cobalt salt is cobalt naphthenate, the reaction kettle is placed in an oven to carry out constant temperature reaction, the temperature of the constant temperature reaction is 150 ℃, the time is 12 hours, the degree of ion replacement can be effectively controlled by adjusting the replacement time, the replacement reaction is incomplete due to too short time, ions cannot be deposited on a substrate, the reaction is naturally cooled to room temperature after the reaction is finished, a product is taken out and repeatedly washed by deionized water and ethanol, and then vacuum drying is carried out in a vacuum drying oven, the vacuum drying temperature is 60 ℃, and the time is 24 hours;
(2) mixing the product of the step (1) with ethylene glycol and Ethylenediamine (EDA) according to the molar ratio of cobalt to ethylene glycol to Ethylenediamine (EDA) in the product of the step (1) of 1:700: 350, and then according to Ni0.85Co0.1Al0.05Adding aluminum salt which is aluminum sulfate into the mixture according to the stoichiometric ratio, placing the mixture into an oven for constant temperature reaction at the temperature of 150 ℃ for 12 hours, introducing aluminum ions by a cation replacement method, naturally cooling to room temperature after the reaction is finished, taking out a product, repeatedly cleaning the product with deionized water and ethanol, and then performing vacuum drying in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to obtain spherical high-nickel ternary nickel cobalt aluminum positive electrode material precursor powder Ni with uniform granularity, high mechanical strength, good conductivity and high porosity0.85Co0.1Al0.05The tap density reaches 2.54g/cm3。
Converted into a molar ratio by detection: and the molar ratio of Ni to Co to Al is =0.85 to 0.1 to 0.05, and is the same as the molar ratio of Ni, Co and Al in the target molecular formula, so that the nickel, cobalt and aluminum are uniformly distributed.
Fig. 1 is a scanning electron microscope image of the product prepared in this example, and it can be seen from the image that the particle morphology of the sample is uniform, and the particle size is relatively uniform, which is about 8 μm.
The product of the embodiment is mixed with lithium hydroxide monohydrate according to the precursor powder Ni of the lithium hydroxide monohydrate and the high-nickel ternary cathode material1-y-xCoyAlxAfter mixing according to the molar ratio of 1.05:1, heating to 500 ℃ at the heating rate of 2 ℃/min in a tube furnace under the oxygen atmosphere, preserving heat for 5h, heating to 750 ℃ at the heating rate of 2 ℃/min, preserving heat for 15h, cooling to room temperature along with the furnace, sintering to obtain an active substance of a positive electrode material, weighing, grinding and uniformly mixing the active substance, PVDF and carbon black in the ratio of 8:1:1 in a drying and dehumidifying environment, adding an NMP solvent, continuously grinding until a thick and uniform slurry is formed, uniformly coating the slurry on a clean aluminum foil, pre-drying at the temperature of 80 ℃ for 0.5h in a coating machine, then continuously drying in a vacuum drying box, keeping the temperature of 80 ℃ for drying for 12h, and finally preparing the slurry with the area of 1.33cm through a sheet punching machine2The positive pole piece of the button cell is obtained and is assembled into a button cell model CR2025 by taking a metal lithium piece as a negative pole, a UH20140 diaphragm of Teklon and a 1mol/L LiPF6/EC + DMC + EMC (the volume ratio of the three is 1:1: 1) solution as an electrolyte in a glove box filled with high-purity argon; first discharge test results at 0.1C (1C =200mAh/g) are plotted as shown in fig. 2.
Example 2
A preparation method of a high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor specifically comprises the following steps:
(1) crushing a nickel net to obtain nickel particles with the particle size of 10-20 mu m, wherein small particles are favorable for the replacement reaction of ions in the solution, ultrasonically cleaning the nickel particles by using a mixed solution of alcohol and deionized water for 7 times, wherein the ratio of the alcohol to the deionized water in the mixed solution is 1:1, mixing the cleaned nickel particles with N, N-Dimethylformamide (DMF) and Ethylenediamine (EDA) in a polytetrafluoroethylene high-pressure reaction kettle according to the molar ratio of nickel to N, N-Dimethylformamide (DMF) to Ethylenediamine (EDA) of 1:120:250, and finally obtaining the high-nickel tri-NNi-Co-Al positive electrode material1-y-xCoyAlxAdding cobalt salt into the mixture according to the stoichiometric ratio, and uniformly stirring and mixing, wherein y =0.05 and x =0.02, namely the molecular formula of the high-nickel ternary nickel cobalt aluminum cathode material is Ni0.93Co0.05Al0.02The cobalt salt is cobalt oxalate, the reaction kettle is placed into an oven to carry out constant temperature reaction, the temperature of the constant temperature reaction is 160 ℃, the time is 10 hours, the degree of ion replacement can be effectively controlled by adjusting the replacement time, the replacement reaction is incomplete due to too short time, ions cannot be deposited on a substrate, the reaction is naturally cooled to room temperature after the reaction is finished, a product is taken out and repeatedly washed by deionized water and ethanol, and then vacuum drying is carried out in a vacuum drying oven, the vacuum drying temperature is 70 ℃, and the time is 15 hours;
(2) mixing the product of the step (1) with ethylene glycol and Ethylenediamine (EDA) according to the molar ratio of cobalt to ethylene glycol to Ethylenediamine (EDA) in the product of the step (1) of 1:900: 450, and then according to Ni0.93Co0.05Al0.02Adding aluminum salt which is aluminum nitrate into the mixture according to the stoichiometric ratio, placing the mixture into an oven for constant temperature reaction at 160 ℃ for 12h, introducing aluminum ions by a cation replacement method, naturally cooling to room temperature after the reaction is finished, taking out a product, repeatedly cleaning the product with deionized water and ethanol, and then performing vacuum drying in a vacuum drying oven at 70 ℃ for 16h to obtain spherical high-nickel ternary nickel cobalt aluminum positive electrode material precursor powder Ni with uniform granularity, high mechanical strength, good conductivity and high porosity0.93Co0.05Al0.02The tap density reaches 2.35g/cm3。
Converted into a molar ratio by detection: and the molar ratio of Ni to Co to Al is =0.93 to 0.05 to 0.02, and is the same as the molar ratio of Ni, Co and Al in the target molecular formula, so that the nickel, cobalt and aluminum are uniformly distributed.
The precursor prepared in this example was subsequently sintered and packaged into a battery according to the method of example 1, and the result curve of the first discharge test of a button cell at 0.1C (1C =200mAh/g) is shown in fig. 3.
Example 3
A preparation method of a high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor specifically comprises the following steps:
(1) crushing a nickel net to 15-25 mu m of nickel particles, wherein small particles are favorable for the replacement reaction of ions in the solution, ultrasonically cleaning the nickel particles by using a mixed solution of alcohol and deionized water for 8 times, wherein the ratio of the alcohol to the deionized water in the mixed solution is 1:1, mixing the cleaned nickel particles with N, N-Dimethylformamide (DMF) and Ethylenediamine (EDA) in a polytetrafluoroethylene high-pressure reaction kettle according to the molar ratio of nickel to N, N-Dimethylformamide (DMF) to Ethylenediamine (EDA) of 1:150:300, and finally obtaining the high-nickel ternary nickel cobalt aluminum positive electrode material Ni1-y-xCoyAlxAdding cobalt salt into the mixture according to the stoichiometric ratio, and uniformly stirring and mixing, wherein y =0.15 and x =0.04, namely the molecular formula of the high-nickel ternary nickel cobalt aluminum cathode material is Ni0.81Co0.15Al0.04The cobalt salt is cobalt acetate, the reaction kettle is placed into an oven to carry out constant temperature reaction, the temperature of the constant temperature reaction is 190 ℃, the time is 6 hours, the degree of ion replacement can be effectively controlled by adjusting the replacement time, the replacement reaction is incomplete due to too short time, ions cannot be deposited on a substrate, the reaction is naturally cooled to room temperature after the reaction is finished, a product is taken out and repeatedly washed by deionized water and ethanol, and then vacuum drying is carried out in a vacuum drying oven, the vacuum drying temperature is 80 ℃, and the time is 12 hours;
(2) mixing the product of the step (1) with ethylene glycol and Ethylenediamine (EDA) according to the molar ratio of cobalt to ethylene glycol to Ethylenediamine (EDA) in the product of the step (1) of 1:800: 380, and then according to Ni0.81Co0.15Al0.04Adding aluminum salt which is aluminum chloride into the mixture according to the stoichiometric ratio, placing the mixture into an oven for constant temperature reaction at 190 ℃ for 6 hours, introducing aluminum ions by a cation replacement method, naturally cooling to room temperature after the reaction is finished, taking out the product, repeatedly cleaning the product with deionized water and ethanol, and then performing vacuum drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the spherical high-porosity product with uniform particle size, high mechanical strength, good conductivity and high porosityPrecursor powder Ni of nickel ternary nickel cobalt aluminum cathode material0.81Co0.15Al0.04The tap density reaches 2.88g/cm3。
Converted into a molar ratio by detection: and the molar ratio of Ni to Co to Al is =0.81 to 0.15 to 0.04, and is the same as the molar ratio of Ni to Co to Al in the target molecular formula, so that the nickel, the cobalt and the aluminum are uniformly distributed.
The precursor prepared in this example was subsequently sintered and packaged into a battery according to the method of example 1, and the result curve of the first discharge test of a button cell at 0.1C (1C =200mAh/g) is shown in fig. 4.
Example 4
A preparation method of a high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor specifically comprises the following steps:
(1) crushing a nickel net to obtain nickel particles with the particle size of about 10-15 mu m, ultrasonically cleaning the nickel particles by using a mixed solution of alcohol and deionized water for 7 times, wherein the ratio of the alcohol to the deionized water in the mixed solution is 1:1, cleaning the nickel particles for 11 minutes each time, mixing the cleaned nickel particles with N, N-Dimethylformamide (DMF) and Ethylenediamine (EDA) in a polytetrafluoroethylene high-pressure reaction kettle according to the molar ratio of nickel (Ni) to N, N-Dimethylformamide (DMF) to Ethylenediamine (EDA) of 1:120:250, and finally obtaining the high-nickel ternary nickel cobalt aluminum positive electrode material Ni1-y-xCoyAlxAdding cobalt salt into the mixture according to the stoichiometric ratio, and uniformly stirring and mixing, wherein y =0.15 and x =0.05, namely the molecular formula of the high-nickel ternary nickel cobalt aluminum cathode material is Ni0.80Co0.15Al0.05The cobalt salt is a mixed salt of cobalt oxalate and cobalt acetate according to a molar ratio of 1:1, the reaction kettle is placed into an oven for constant temperature reaction, the temperature of the constant temperature reaction is 180 ℃, the time is 7 hours, the degree of ion replacement can be effectively controlled by adjusting the replacement time, the replacement reaction is incomplete due to too short time, ions cannot deposit on a substrate, the reaction product is naturally cooled to room temperature after the reaction is finished, the product is taken out and repeatedly cleaned by deionized water and ethanol, and then vacuum drying is carried out in a vacuum drying oven, the vacuum drying temperature is 70 ℃, and the vacuum drying time is 15 hours;
(2) mixing the product of the step (1) with ethylene glycol and ethylene glycolMixing amines (EDA) according to the molar ratio of cobalt to ethylene glycol to Ethylenediamine (EDA) in the product of step (1) of 1:780: 400, and then according to Ni0.80Co0.15Al0.05Adding aluminum salt which is aluminum nitrate into the mixture according to the stoichiometric ratio, placing the mixture into an oven for constant temperature reaction at the temperature of 150 ℃ for 12h, introducing aluminum ions by a cation replacement method, naturally cooling to room temperature after the reaction is finished, taking out the product, repeatedly cleaning the product with deionized water and ethanol, and then performing vacuum drying in a vacuum drying oven at the temperature of 80 ℃ for 12h to obtain spherical high-nickel ternary nickel cobalt aluminum positive electrode material precursor powder Ni with uniform granularity, high mechanical strength, good conductivity and high porosity0.80Co0.15Al0.05The tap density reaches 2.66g/cm3。
Converted into a molar ratio by detection: and the molar ratio of Ni to Co to Al is =0.80 to 0.15 to 0.05, and is the same as the molar ratio of Ni, Co and Al in the target molecular formula, so that the nickel, cobalt and aluminum are uniformly distributed.

Claims (7)

1. A preparation method of a high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor is characterized by comprising the following steps:
(1) mixing the cleaned nickel particles with N, N-dimethylformamide and ethylenediamine, and obtaining the high-nickel ternary nickel cobalt aluminum cathode material Ni1-y-xCoyAlxAdding cobalt salt according to the stoichiometric ratio, stirring and uniformly mixing, wherein y is more than 0 and less than or equal to 0.15, x is more than 0 and less than or equal to 0.05, placing the mixture into a polytetrafluoroethylene high-pressure reaction kettle, placing the polytetrafluoroethylene high-pressure reaction kettle into an oven for constant-temperature reaction, naturally cooling to room temperature after the reaction is finished, taking out a product, repeatedly cleaning with deionized water and ethanol, and then drying in vacuum;
(2) mixing the product of the step (1) with ethylene glycol and ethylenediamine, and then mixing according to Ni1-y-xCoyAlxAdding aluminum salt into the mixture according to the stoichiometric ratio, placing the mixed substance into a polytetrafluoroethylene high-pressure reaction kettle, and placing the polytetrafluoroethylene high-pressure reaction kettle into a baking ovenAnd carrying out constant-temperature reaction in the box, wherein the constant-temperature reaction temperature is 150-190 ℃, the time is 6-12 h, naturally cooling to room temperature after the reaction is finished, taking out the product, repeatedly cleaning with deionized water and ethanol, and then carrying out vacuum drying to obtain the precursor powder of the high-nickel ternary nickel-cobalt-aluminum positive electrode material.
2. The preparation method of the high-nickel ternary nickel-cobalt-aluminum cathode material precursor according to claim 1, wherein the nickel particles in the step (1) are particles with a particle size of 5-25 μm after the nickel mesh is crushed, ultrasonic cleaning is performed on the nickel particles by using a mixed solution of alcohol and deionized water, the cleaning frequency is not less than 6 times, each time lasts for 10-15 minutes, and the ratio of the alcohol to the deionized water in the mixed solution is 1: 1.
3. The preparation method of the high-nickel ternary nickel cobalt aluminum cathode material precursor according to claim 1, wherein the nickel particles in the step (1) are mixed with N, N-dimethylformamide and ethylenediamine according to a molar ratio of nickel to N, N-dimethylformamide to ethylenediamine of 1:100 to 150: 200 to 300.
4. The preparation method of the high-nickel ternary nickel cobalt aluminum cathode material precursor according to claim 1, wherein the cobalt salt in the step (1) is one or a mixture of several of cobalt naphthenate, cobalt oxalate and cobalt acetate in any proportion.
5. The preparation method of the high-nickel ternary nickel-cobalt-aluminum cathode material precursor according to claim 1, wherein the vacuum drying temperature in the step (1) and the step (2) is 60-80 ℃, and the time is 12-24 hours.
6. The preparation method of the high-nickel ternary nickel cobalt aluminum cathode material precursor according to claim 1, wherein the product obtained in the step (1) in the step (2) is mixed with ethylene glycol and ethylenediamine according to a molar ratio of cobalt to ethylene glycol to ethylene diamine in the product obtained in the step (1) of 1: 700-900: 350-450.
7. The method for preparing the high-nickel ternary nickel-cobalt-aluminum cathode material precursor as claimed in claim 1, wherein the aluminum salt in step (2) is aluminum sulfate, aluminum nitrate, sodium metaaluminate or aluminum chloride.
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