CN107834064B - High-nickel small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof - Google Patents

High-nickel small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof Download PDF

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CN107834064B
CN107834064B CN201711260819.1A CN201711260819A CN107834064B CN 107834064 B CN107834064 B CN 107834064B CN 201711260819 A CN201711260819 A CN 201711260819A CN 107834064 B CN107834064 B CN 107834064B
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nickel
cobalt
reaction kettle
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CN107834064A (en
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张鑫
佘圣贤
朱珠
徐乾松
李扬
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Ningbo Rongbai Material Technology Co Ltd
Ningbo Ronbay Lithium Battery Material Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a high-nickel small-particle-size nickel-cobalt-manganese hydroxide and a preparation method thereof, wherein the preparation method comprises the following steps: (1) continuously introducing a nickel-cobalt-manganese mixed metal solution, a precipitator and a complexing agent for nucleation under the conditions of more mother liquor and high complexing agent concentration, and highly dispersing crystal nuclei through high-speed stirring to enter a crystal nucleus growth stage; (2) when the reaction is started until the material can be precipitated, when D50 is 1.3-1.5 mu m, extracting feed liquid with the effective volume of 1/6-1/3 from the upper part of the reaction kettle, pouring out supernatant liquid when the feed liquid is completely precipitated, and returning the precipitate to the reaction kettle for continuous reaction; (3) the procedure was repeated to introduce new seeds and increase the solids content, and the reaction was stopped until D50 ═ 3 μm. The method adopts nucleation crystallization/new seed crystal introduction to prepare the nickel-cobalt-manganese hydroxide, can avoid artificial balling, does not need to modify the existing reaction kettle, is simple and convenient to operate, and can enlarge production; the prepared nickel-cobalt-manganese hydroxide has uniform and concentrated particle size distribution, no agglomeration, high tap density and good sphericity.

Description

High-nickel small-particle-size nickel-cobalt-manganese hydroxide and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to high-nickel small-particle-size nickel-cobalt-manganese hydroxide and a preparation method thereof.
Background
Since the lithium ion battery was first developed and succeeded by Sony corporation in 1990, the lithium ion battery has wide application prospects and potential huge economic benefits in the aspects of portable electronic equipment, electric automobiles, national defense technologies, space technologies and the like because of the main advantages of high voltage and high capacity and the remarkable characteristics of long cycle life and good safety performance, and quickly becomes a research hotspot which is widely concerned at present. In the structural combination of lithium ion materials, the high nickel positive electrode material has been paid attention to due to its high capacity, and has become the focus of the current research, especially the high nickel positive electrode small particles with high energy, high multiplying power and high safety performance are most concerned.
The key to the preparation of the high-nickel anode small particles lies in the preparation of a small-particle-size nickel-cobalt-manganese hydroxide precursor; the precursor has good sphericity, uniform particle size dispersion, no agglomeration and high tap density, and can be used as a matrix to prepare the high-nickel anode small-particle material with good performance.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the technical defects of the background technology and provides a high-nickel small-particle-size nickel-cobalt-manganese hydroxide and a preparation method thereof. In the invention, under the conditions of high ammonia water concentration and high rotating speed, artificial ball hitting can be avoided by nucleating crystallization/introducing new seed crystals and increasing solid content; the preparation method of the invention does not need to modify the existing reaction kettle, is simple and convenient to operate and can enlarge the production; the high-nickel small-particle-size nickel-cobalt-manganese hydroxide prepared by the method has uniform particle size distribution, concentration, no agglomeration, high tap density and good sphericity; the high-nickel small-particle-size nickel cobalt manganese hydroxide D50 is 1.5-3 mu m, the particle size distribution is 1-10 mu m, and the tap density is 1.6-2.4 g/cm 3; the lithium ion battery anode material prepared from the high-nickel small-particle-size nickel-cobalt-manganese hydroxide has high capacity, high tap density, centralized particle size distribution and good single crystal morphology.
The technical means adopted by the invention for solving the technical problems is as follows:
a preparation method of high-nickel small-particle-size nickel-cobalt-manganese hydroxide comprises the following steps:
(1) the nickel-cobalt-manganese soluble salt is prepared according to the mol ratio of nickel-cobalt-manganese in the hydroxide, namely according to the general formula Ni1-x- yCoxMny(OH)2Wherein x is more than or equal to 0.09 and less than or equal to 0.12, and y is more than or equal to 0.03 and less than or equal to 0.05, and preparing a first mixed metal salt solution containing Ni ions, Co ions and Mn ions; preparing a second mixed solution consisting of a precipitator; preparing a third mixed solution consisting of complexing agents;
(2) adding pure water with the effective volume of 80% into the reaction kettle under the stirring condition, introducing the second mixed solution and the third mixed solution in the step (1) to prepare mother liquor, and continuously introducing inert gas as protection;
(3) enabling the first mixed metal salt solution, the second mixed solution and the third mixed solution in the step (1) to flow in parallel, continuously introducing into a high-speed stirring reaction kettle, and carrying out coprecipitation reaction under the action of the second mixed solution and the third mixed solution, wherein crystal nuclei are continuously formed and grown; when the granularity reaches 1.3-1.5 mu m, feeding continuously, pumping the feed liquid from the upper part of the reaction kettle, pouring out the supernatant after the feed liquid is precipitated, pouring the precipitate back to the reaction kettle, then adopting the same method when the reaction kettle is full, introducing new seed crystals, increasing the solid content, slowing down the growth rate of particles, avoiding the adverse conditions of small particle agglomeration and the like caused by artificial balling, stopping feeding when the granularity D50 reaches 2.5-3 mu m, and finishing the reaction;
(4) and (4) sequentially aging the reaction products obtained in the step (3), carrying out alkaline washing centrifugation on the aged slurry, and then drying, crushing, sieving and removing iron to obtain the high-nickel small-particle-size nickel-cobalt-manganese hydroxide.
In the technical scheme, the materials are continuously discharged and fed back in the reaction process, so that new seed crystals are introduced and the solid content is increased, and the adverse conditions of small particle agglomeration and the like caused by artificial balling can be avoided.
In the technical scheme, the feed liquid is continuously introduced in the reaction process, the continuous production is realized, and the productivity is not reduced.
Preferably, in the step (1), the concentration of the first mixed metal salt solution is 1.5-2 mol/L.
Preferably, in the step (1), the precipitant is KOH, LiOH, NaOH, Na2CO3Further preferably NaOH.
Preferably, in the step (1), the concentration of the second mixed solution is 2-6 mol/L.
Preferably, in the step (1), the complexing agent is any one or more of ammonia water, disodium ethylene diamine tetraacetate, sulfosalicylic acid and glycine, and further preferably ammonia water.
Preferably, in the step (1), the concentration of the third mixed solution is 7-14 mol/L.
Preferably, in the step (2), the mother liquor accounts for more than 80% of the effective volume of the reaction kettle, wherein the pH value is 12.0-12.4, the ammonia value is 10-12 g/L, and the temperature is 40-65 ℃.
Preferably, in the step (2), the value of the third mixed solution in the reaction kettle system is 8-14 g/L.
Preferably, in the step (2), the inert gas is one or both of nitrogen and argon.
Preferably, in the step (3), the coprecipitation reaction temperature is 40-65 ℃.
Preferably, in the step (3), the pH of the coprecipitation reaction is 11.0-12.6.
Preferably, in the step (3), the rotation speed during the coprecipitation reaction is 700-1200 rpm.
Preferably, in the step (3), the volume of the feed liquid extracted from the upper part of the reaction kettle accounts for 1/6-1/3 of the effective volume of the reaction kettle.
More preferably, in the step (3), the volume of the feed liquid extracted from the upper part of the reaction kettle accounts for 1/4 of the effective volume of the reaction kettle.
Preferably, in the step (4), the aging time is 45-85 min.
Preferably, in the step (4), the temperature of the alkaline washing is 50-85 ℃.
Preferably, in the step (4), the drying temperature is 100-150 ℃.
Preferably, in the step (4), the high-nickel small-particle-size nickel cobalt manganese hydroxide D50 is 1.5-3 μm.
Preferably, in the step (4), the particle size distribution of the high-nickel small-particle-size nickel-cobalt-manganese hydroxide is 1-10 μm, and the tap density is 1.6-2.4 g/cm 3.
The high-nickel small-particle-size nickel-cobalt-manganese hydroxide is prepared by the method, wherein the high-nickel small-particle-size nickel-cobalt-manganese hydroxide D50 is 1.5-3 mu m, the particle size distribution is 1-10 mu m, and the tap density is 1.6-2.4 g/cm 3; the high-nickel small-particle-size nickel-cobalt-manganese hydroxide has the advantages of good sphericity, uniform particle size distribution, no agglomeration and high tap density.
And sintering the high-nickel small-particle-size nickel cobalt manganese hydroxide at 700-1000 ℃ for 24-27 h to obtain the lithium ion battery anode material.
The lithium ion battery anode material has high capacity, high tap density, concentrated particle size distribution and good single crystal morphology.
The basic principle of the invention is as follows:
the invention adopts nucleation crystallization/new seed crystal introduction to prepare the high nickel small particle size hydroxide:
(1) continuously introducing a nickel-cobalt-manganese mixed metal solution, a precipitator and a complexing agent for nucleation under the conditions of more mother liquor and high complexing agent concentration, and highly dispersing crystal nuclei through high-speed stirring to enter a crystal nucleus growth stage;
(2) when the reaction is started until the materials can be precipitated, and D50 is 1.3-1.5 mu m, extracting feed liquid with the effective volume of 1/4 from the upper part of the reaction kettle, pouring out supernatant liquid when the feed liquid is completely precipitated, and returning the precipitate to the reaction kettle for continuous reaction;
(3) the procedure was repeated to introduce new seeds and increase the solids content, and the reaction was stopped until D50 ═ 3 μm.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) in the invention, under the conditions of high ammonia water concentration and high rotating speed, artificial ball hitting can be avoided by nucleating crystallization/introducing new seed crystals and increasing solid content;
(2) the preparation method of the invention does not need to modify the existing reaction kettle, is simple and convenient to operate and can enlarge the production;
(3) the high-nickel small-particle-size nickel-cobalt-manganese hydroxide prepared by the method has uniform particle size distribution, concentration, no agglomeration, high tap density and good sphericity;
(4) the high-nickel small-particle-size nickel-cobalt-manganese hydroxide D50 prepared by the method is 1.5-3 mu m, the particle size distribution is 1-10 mu m, and the tap density is 1.6-2.4 g/cm 3;
(5) the lithium ion battery anode material prepared from the high-nickel small-particle-size nickel-cobalt-manganese hydroxide has high capacity, high tap density, centralized particle size distribution and good single crystal morphology.
Drawings
FIG. 1 is an SEM image of high-nickel small-particle-size nickel cobalt manganese hydroxide prepared in example 1 of the present invention;
FIG. 2 is a photograph showing the particle size distribution of the high nickel small particle size nickel cobalt manganese hydroxide prepared in example 1 of the present invention;
FIG. 3 is an SEM image of high-nickel small-particle-size nickel cobalt manganese hydroxide prepared in example 2 of the present invention;
FIG. 4 is a photograph of the particle size distribution of the high nickel small particle size nickel cobalt manganese hydroxide prepared in example 2 of the present invention;
fig. 5 is an SEM image of a lithium ion battery positive electrode material prepared using the high nickel small particle size nickel cobalt manganese hydroxide prepared in example 1 of the present invention as a base material.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It is to be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. Moreover, it should be understood that the invention is not limited to the above-described embodiments, but is capable of various modifications and changes within the scope of the invention.
The invention provides a preparation process of high-nickel small-particle-size nickel-cobalt-manganese hydroxide, which comprises the following steps of:
(1) the nickel-cobalt-manganese soluble salt is prepared according to the mol ratio of nickel-cobalt-manganese in the hydroxide, namely according to the general formula Ni1-x- yCoxMny(OH)2Wherein x is more than or equal to 0.09 and less than or equal to 0.12, and y is more than or equal to 0.03 and less than or equal to 0.1, and a first mixed metal salt solution with the total concentration of Ni, Co and Mn ions of 1.5-2.0 mol/L is prepared;
preparing a second mixed solution with the concentration of 2-6 mol/L of a sodium hydroxide precipitator;
preparing a third mixed solution with the concentration of the ammonia water complexing agent being 7-14 mol/L;
(2) adding pure water with the effective volume of 80% into a reaction kettle under the stirring condition, introducing a complexing agent and a precipitating agent to prepare a mother solution, and continuously introducing certain nitrogen as protection;
(3) and (3) continuously introducing the prepared three solutions into a reaction kettle in a parallel flow manner, and carrying out coprecipitation reaction under the action of sodium hydroxide and ammonia water. Feeding continuously when the particle size reaches 1.5 mu m, pumping 1/4 feed liquid from the upper part of the reaction kettle, pouring out supernatant after precipitation, pouring the material back to the reaction kettle, then adopting the same method when the reaction kettle is full, introducing new seed crystal by the method, increasing the solid content of the system in the kettle, slowly increasing the particle size, avoiding artificial balling, stopping feeding when the particle size D50 reaches 2.5-3 mu m, and finishing the reaction;
the coprecipitation reaction temperature is 40-65 ℃;
the pH value of the coprecipitation reaction is 11.0-12.6;
the co-precipitation rotating speed is 700-1200 rpm;
the inert gas is one or two of nitrogen or argon;
the initial reaction mother liquor accounts for more than 80% of the effective volume of the kettle body, wherein the pH value is 12.0-12.4, the ammonia value is 10-12 g/L, and the temperature is 40-65 ℃;
(4) sequentially aging, washing and drying the obtained reaction product to obtain high-nickel small-particle-size nickel-cobalt-manganese hydroxide;
the aging time is 45-85 min;
the washing temperature is 50-85 ℃;
the drying temperature is 100-150 ℃.
Example 1
Dissolving nickel sulfate, cobalt sulfate and manganese sulfate with water to prepare a sulfate aqueous solution with the total concentration of three ions of Ni, Co and Mn being 1.5mol/L, wherein the ratio of nickel, cobalt and manganese is Ni, Co and Mn being 0.83, 0.12 and 0.05; preparing a second mixed solution with the concentration of sodium hydroxide of 4 mol/L; preparing a third mixed solution with the ammonia water concentration of 9 mol/L;
40L of deionized water is added into a 50L reaction kettle, and a sodium hydroxide solution and ammonia water are introduced to prepare a mother solution with the pH value of 12.4, the ammonia value of 10g/L and the temperature of 50 ℃. Adjusting the rotating speed of the reaction kettle to 900r/min, starting stirring, introducing nitrogen into the reaction kettle for atmosphere protection, and continuously introducing nitrogen in the whole reaction process;
continuously introducing the prepared three solutions into a reaction kettle through a precisely-metered peristaltic pump at the same time to perform a nucleation growth reaction, controlling the pH value of the system to be 12.2-12.3, controlling the ammonia value to be 10-11 g/L, and controlling the reaction time to be 10 h; after the feeding reaction is carried out for a period of time, when the feed liquid discharged into the beaker can be completely precipitated, the pH value is gradually reduced to about 12.2;
continuously reacting until the granularity D50 of the material in the kettle is 1.3-1.5 mu m, beginning to extract 1/4 feed liquid from the upper part of the reaction kettle, pouring out supernatant after precipitation, pouring the material back to the reaction kettle, and then adopting the same method every two hours to introduce new seed crystals, so that the solid content in the kettle is increased, the granularity is slowly increased, and meanwhile, artificial ball hitting can be avoided; when the granularity grows to 2.0 mu m, adjusting the rotating speed to 1200r/min, adjusting the pH value of the system to 12.1-12.2 and the ammonia value to 11-11.5 g/L, continuing to react until the granularity D50 reaches about 2.5 mu m, stopping feeding, continuing to stir for 1h, discharging, washing and drying;
aging the slurry obtained after coprecipitation for 1h, performing solid-liquid separation, putting the cake-shaped solid into a washing kettle with the temperature of 60 ℃ and the volume of 1m3, simultaneously adding 10mol/L of caustic soda into the washing kettle, washing, centrifuging, and drying in a forced air drying oven at the temperature of 130 ℃ for 20h until the moisture meets the requirement;
scanning electron microscope detection is carried out on the high-nickel small-particle-size nickel-cobalt-manganese hydroxide obtained in the embodiment 1 of the invention, and the detection result is shown in fig. 1, so that the high-nickel small-particle-size nickel-cobalt-manganese hydroxide prepared in the embodiment 1 of the invention has the advantages of good sphericity, uniform particle size distribution and no agglomeration;
the particle size test of the high nickel small particle size nickel cobalt manganese hydroxide obtained in the embodiment 1 of the present invention is performed, and the detection result is shown in fig. 2, which shows that the particle size distribution of the high nickel small particle size nickel cobalt manganese hydroxide obtained in the embodiment 1 of the present invention is concentrated without agglomeration, and D50 is 2.79 μm;
tap density test is carried out on the high-nickel small-particle-size nickel-cobalt-manganese hydroxide obtained in the embodiment 1 of the invention, and the detection result shows that the tap density of the prepared high-nickel small-particle-size nickel-cobalt-manganese hydroxide is 2.24g/cm3, and the specific surface area is 4.5976m2/g;
Example 2
Dissolving nickel sulfate, cobalt sulfate and manganese sulfate with water to prepare a sulfate aqueous solution with the total concentration of Ni, Co and Mn being 2.0mol/L, wherein the ratio of nickel, cobalt and manganese is Ni, Co and Mn being 0.88, 0.09 and 0.03; preparing a second mixed solution with the concentration of 6mol/L of sodium hydroxide; preparing a third mixed solution with the ammonia water concentration of 12 mol/L;
150L of deionized water is added into a 200L reaction kettle, and a sodium hydroxide solution and ammonia water are introduced to prepare a mother solution with the pH value of 12.5, the ammonia value of 9g/L and the temperature of 50 ℃. Adjusting the rotating speed of the reaction kettle to 700r/min, starting stirring, introducing nitrogen into the reaction kettle for atmosphere protection, and continuously introducing nitrogen in the whole reaction process;
continuously introducing the prepared three solutions into a reaction kettle through a precisely-metered peristaltic pump at the same time to perform a nucleation growth reaction, controlling the pH value of the system to be 12.1-12.2, controlling the ammonia value to be 10-11 g/L, and controlling the reaction time to be 10 h; after the feeding reaction is carried out for a period of time, when the feed liquid discharged into the beaker can be completely precipitated, the pH value is gradually reduced to about 12.1;
continuously reacting until the granularity D50 of the material in the kettle is 1.3-1.5 mu m, beginning to extract 1/4 feed liquid from the upper part of the reaction kettle, pouring out supernatant after precipitation, pouring the material back to the reaction kettle, and then adopting the same method every two hours to introduce new seed crystals, so that the solid content in the kettle is increased, the granularity is slowly increased, and meanwhile, artificial ball hitting can be avoided; when the granularity grows to 2.0 mu m, adjusting the rotating speed to 900r/min, adjusting the pH value of the system to 12.0-12.1 and the ammonia value to 11-11.5 g/L, continuing to react until the granularity D50 reaches about 2.5 mu m, stopping feeding, continuing to stir for 1h, discharging, washing and drying;
aging the slurry obtained after coprecipitation for 1h, performing solid-liquid separation, putting the cake-shaped solid into a washing kettle with the temperature of 60 ℃ and the volume of 1m3, simultaneously adding 10mol/L of caustic soda into the washing kettle, washing, centrifuging, and drying in a forced air drying oven at the temperature of 130 ℃ for 20h until the moisture meets the requirement;
scanning electron microscope detection is carried out on the high-nickel small-particle-size nickel-cobalt-manganese hydroxide obtained in the embodiment 2 of the invention, and the detection result is shown in fig. 3, so that the high-nickel small-particle-size nickel-cobalt-manganese hydroxide prepared in the embodiment 2 of the invention has good sphericity, uniform particle size distribution and no agglomeration;
the particle size test of the high nickel small particle size nickel cobalt manganese hydroxide obtained in the embodiment 2 of the present invention is performed, and the detection result is shown in fig. 4, which shows that the particle size distribution of the high nickel small particle size nickel cobalt manganese hydroxide obtained in the embodiment 2 of the present invention is concentrated without agglomeration, and D50 is 2.82 μm;
tap density test is carried out on the high-nickel small-particle-size nickel-cobalt-manganese hydroxide obtained in the embodiment 2 of the invention, and the detection result shows that the tap density of the prepared high-nickel small-particle-size nickel-cobalt-manganese hydroxide is 1.91g/cm3Specific surface area of 6.4874m2/g;
According to the embodiment, the invention provides a preparation method of high-nickel small-particle-size nickel-cobalt-manganese hydroxide, under the conditions of more mother liquor, high ammonia water concentration and high rotation speed, nickel-cobalt-manganese mixed metal solution, sodium hydroxide and ammonia water are continuously introduced for nucleation, after nucleation, crystal nuclei are highly dispersed through high-speed stirring, the crystal nuclei enter a crystal nucleus growth stage, in the initial growth stage, a part of feed liquid is discharged from a reaction kettle, supernatant liquid is removed, and precipitates are poured back to the reaction kettle, so that the solid content is increased, new seed crystals are introduced, the phenomenon of particle agglomeration caused by excessive small particles due to artificial balling is avoided, and finally small hydroxide particles with uniform particle size distribution, no agglomeration, good sphericity and high tap density D50 of 1.5-3 μm are obtained. The preparation method of the high-nickel small-particle-size single crystal nickel cobalt manganese hydroxide provided by the invention has the advantages that the solid content is increased, new seed crystals are introduced, the high-nickel small particles with concentrated particle size distribution, no agglomeration, high tap density and good sphericity are formed under the conditions of high ammonia water concentration and high rotating speed, the existing reaction kettle is not required to be modified, the operation is simple and convenient, and the production can be enlarged.
The invention also provides a method for preparing the lithium ion battery anode material by using the high-nickel small-particle-size nickel-cobalt-manganese hydroxide prepared by the technical scheme of the embodiment 1 as the base material. The lithium source used for preparing the cathode material is battery-grade lithium hydroxide; the sintering temperature of the lithium ion battery anode material is 700-1000 ℃, and the sintering time is 24-27 h; the lithiation ratio of the lithium ion battery anode material, namely Li (Ni + Co + Mn) is 1.05; the 0.1C and 4.3V half-capacitance of the lithium ion battery anode material is 215.3 mAh/g;
fig. 5 is an SEM photograph of the above lithium ion battery positive electrode material.
The above description is not intended to limit the invention, nor is the invention limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the spirit of the invention.

Claims (5)

1. A preparation method of high-nickel small-particle-size nickel-cobalt-manganese hydroxide is characterized by comprising the following steps of:
(1) the nickel-cobalt-manganese soluble salt is prepared according to the mol ratio of nickel-cobalt-manganese in the hydroxide, namely according to the general formula Ni1-x-yCoxMny(OH)2Wherein x is more than or equal to 0.09 and less than or equal to 0.12, and y is more than or equal to 0.03 and less than or equal to 0.05, and preparing a first mixed metal salt solution containing Ni ions, Co ions and Mn ions; preparing a second mixed solution consisting of a precipitator; preparing a third mixed solution consisting of complexing agents;
(2) adding pure water with the effective volume of 80% into the reaction kettle under the stirring condition, introducing the second mixed solution and the third mixed solution in the step (1) to prepare mother liquor, and continuously introducing inert gas as protection;
(3) enabling the first mixed metal salt solution, the second mixed solution and the third mixed solution in the step (1) to flow in parallel, continuously introducing into a high-speed stirring reaction kettle, and carrying out coprecipitation reaction under the action of the second mixed solution and the third mixed solution; continuing feeding when the particle size reaches 1.3-1.5 mu m, pumping the feed liquid from the upper part of the reaction kettle, pouring out the supernatant after the feed liquid is precipitated, pouring the precipitate back to the reaction kettle, then adopting the same method when the reaction kettle is full, introducing new seed crystals, stopping feeding when the particle size D50 reaches 2.5-3 mu m, and finishing the reaction;
(4) sequentially aging the reaction products obtained in the step (3), carrying out alkaline washing centrifugation on the aged slurry, and then drying, crushing, sieving and removing iron to obtain high-nickel small-particle-size nickel-cobalt-manganese hydroxide;
in the step (1), the concentration of the first mixed metal salt solution is 1.5-2 mol/L, the concentration of the second mixed solution is 2-6 mol/L, and the concentration of the third mixed solution is 7-14 mol/L;
in the step (2), the value of the third mixed solution in the reaction kettle system is 8-14 g/L;
in the step (2), the mother liquor accounts for more than 80% of the effective volume of the reaction kettle, wherein the pH value is 12.0-12.4, the ammonia value is 10-12 g/L, and the temperature is 40-65 ℃;
in the step (3), the temperature of the coprecipitation reaction is 40-65 ℃, the pH value of the coprecipitation reaction is 11.0-12.6, and the rotating speed of the coprecipitation reaction is 700-1200 rpm;
in the step (3), the volume of the feed liquid extracted from the upper part of the reaction kettle accounts for 1/6-1/3 of the effective volume of the reaction kettle.
2. The method for preparing nickel cobalt manganese hydroxide with high nickel content and small particle size as claimed in claim 1, wherein in the step (1), the complexing agent is any one or more of ammonia water, disodium ethylene diamine tetraacetate, sulfosalicylic acid and glycine.
3. The method for preparing nickel cobalt manganese hydroxide with high nickel content and small particle size as claimed in claim 1, wherein in the step (4), the aging time is 45-85 min, the alkali washing temperature is 50-85 ℃, and the drying temperature is 100-150 ℃.
4. A high-nickel small-particle-size nickel-cobalt-manganese hydroxide, which is characterized by being prepared by the method of any one of claims 1 to 3.
5. The high-nickel small-particle-size nickel-cobalt-manganese hydroxide as claimed in claim 4, wherein the high-nickel small-particle-size nickel-cobalt-manganese hydroxide D50 is 1.5-3 μm, the particle size distribution is 1-10 μm, and the tap density is 1.6-2.4 g/cm3
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CN110931776B (en) * 2019-12-24 2021-02-02 中南大学 Preparation method of nickel-cobalt-manganese ternary positive electrode material precursor with multi-level distribution of particle sizes
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CN114645329B (en) * 2022-03-30 2023-08-01 宁波容百新能源科技股份有限公司 Nickel-cobalt-manganese hydroxide with high nickel and low cobalt fine whisker and preparation method thereof
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