CN115520906B - Narrow-distribution large-particle nickel cobalt manganese hydroxide and preparation method thereof - Google Patents

Narrow-distribution large-particle nickel cobalt manganese hydroxide and preparation method thereof Download PDF

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CN115520906B
CN115520906B CN202110703316.7A CN202110703316A CN115520906B CN 115520906 B CN115520906 B CN 115520906B CN 202110703316 A CN202110703316 A CN 202110703316A CN 115520906 B CN115520906 B CN 115520906B
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杨亚强
李肖萌
宋梦桃
李作伟
孔科伟
王海迪
毛阳俊
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Huayou New Energy Technology Quzhou Co ltd
Zhejiang Huayou Cobalt Co Ltd
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Zhejiang Huayou Cobalt Co Ltd
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Abstract

The invention discloses a narrow-distribution large-particle nickel cobalt manganese hydroxide and a preparation method thereof. The invention adopts low temperature, low pH and low raw material flow to obtain seed crystals with proper quantity and larger grain diameter, greatly improves the raw material flow, forms a loose porous inner layer, controls the reaction time and inhibits the cracking of grains; the temperature, the pH value and the stirring power in unit volume are gradually reduced, the generation of small particles is restrained, the porosity is controlled through oxidation, the phenomenon that primary particles are excessively densely stacked due to high solid content is avoided, and an outer layer which is compact and contains a small amount of pores is obtained; the product has concentrated particle size distribution, no oversized particles and undersized particles, can ensure the consistency of the charging and discharging processes of each particle, and effectively avoids the overstock and overstock of the understock, thereby improving the material circulation performance; the prepared nickel cobalt manganese hydroxide primary particles are in a special long strip shape, so that the porosity is proper, the reduction of the impurity content of Na, S and the like in the washing process is facilitated, and the electrochemical performance of the obtained positive electrode material is improved.

Description

Narrow-distribution large-particle nickel cobalt manganese hydroxide and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery anode material precursors, and particularly relates to a narrow-distribution large-particle nickel cobalt manganese hydroxide and a preparation method thereof.
Background
Currently, the nickel-cobalt-manganese ternary cathode material has good market prospect and high development potential in the field of power batteries. The performance of ternary cathode materials (lithium nickel cobalt manganese oxide) depends largely on the performance of ternary precursors (e.g., nickel cobalt manganese hydroxide), wet co-precipitation being a common method for preparing nickel cobalt manganese hydroxide. The size, morphology, structure and the like of the nickel cobalt manganese hydroxide have direct influence on the technical indexes of the nickel cobalt lithium manganate.
At present, the highest compaction density combination is obtained by blending the large and small particles with different gradations, so that the energy density of the battery can be effectively improved. In order to meet the grading effect and stable performance, the particle size distribution of the large particle precursor used in the process is as narrow as possible. Typically, a precursor with a narrow particle size distribution is co-precipitated by a batch wet process, but this process currently has the following problems:
(1) Because the synthesis growth period of large particles is long, partial seed crystals need to be transferred in the synthesis process, otherwise, the particle size grows slowly and cannot reach the target particle size; or synthesizing large particles by adopting seed crystals with certain granularity, but the method needs to prepare the seed crystals first, so that the operation is complicated;
(2) In the synthesis process, due to the continuous increase of the solid content in the reaction system, small particles are inevitably generated, so that the particle size distribution is widened, and the generated small particles still exist in the prepared positive electrode material, are more prone to overcharging or overdischarging, and seriously influence the specific capacity and the cycle performance of the material;
(3) The method for reducing the generation of small particles is commonly used at present, namely, the solid content of synthesis shutdown is reduced, but the method seriously affects the productivity, so that the synthesis productivity is low, the production efficiency is reduced, and the cost is increased;
(4) After the particle size grows to a certain stage, the particle surface is smoother and smoother under the actions of stirring and collision among particles due to the increase of the solid content, crystal faces required by the particle growth are blurred, new crystal nuclei are difficult to adhere to the surface of large particles to continue to grow, the particle size growth speed in a system is slow, and large-particle-size precursor particles cannot be obtained.
How to obtain large-particle precursor with narrow particle size distribution under the condition of not sacrificing precursor productivity, and realize smooth process, simple control and high productivity of the large-particle precursor is a problem to be solved urgently.
Disclosure of Invention
The invention aims at providing a nickel cobalt manganese hydroxide with narrow distribution and large particles, and the particle size distribution of the nickel cobalt manganese hydroxide is concentrated. Firstly, the particle size distribution of nickel cobalt lithium manganate particles prepared by taking the nickel cobalt lithium manganate as a precursor is concentrated, and the nickel cobalt lithium manganate particles have no oversized particles and undersized particles, so that the consistency of the charging and discharging processes of all the particles can be ensured, the overcharge and overdischarge when the undersized particles exist can be effectively avoided, and the recycling performance of the material can be improved; secondly, the primary particles of the large particles prepared by the method are in a special long strip shape, so that the porosity is proper, the reduction of the impurity content of Na, S and the like in the washing process is facilitated, and the electrochemical performance of the obtained anode material is improved; meanwhile, when the material is sintered with a lithium source, the material has good connectivity and permeability due to vacancies caused by the special 'slender strip' shape, is favorable for fully contacting with the lithium source in the sintering process, has higher reaction activity, can be sintered at a low temperature, reduces Li/Ni mixed discharge, and improves the cycle performance and the multiplying power performance to a certain extent; in addition, if other elements are doped, the product is more beneficial to the uniform permeation of the doped elements, and the cycle stability after doping is obviously improved; finally, the product with proper porosity can be used for preparing the anode material with proper porosity, is more beneficial to electrolyte infiltration, provides more shortcut channels for lithium ion migration in the charge and discharge process, reduces the diffusion impedance of lithium ions, and obviously improves the rate capability.
Therefore, the invention adopts the following technical scheme: the nickel cobalt manganese hydroxide is represented by a general formula Ni xCoyMnz(OH)2, wherein x+y+z=1, the values of x, y and z are all 0-1, and x, y and z are not equal to 0 and 1; the nickel cobalt manganese hydroxide is a similar spherical particle in microscopic morphology measured by a scanning electron microscope, D50 is 8.0-20.0 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3, and particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50 measured by a laser particle size analysis diffraction method.
Further, the inside of the nickel cobalt manganese hydroxide particles was in a radial shape, and a section taken by cutting the particles with an argon ion beam showed that the particles exhibited a porous internal structure.
Further, the primary particles of the nickel cobalt manganese hydroxide are in a strip shape with clear textures, the length of the strip is 80-500 nm, and the width of the strip is 30-250 nm.
Further, the nickel cobalt manganese hydroxide particles are divided into an inner layer and an outer layer, the diameter of the inner layer is 1.0-8.0 mu m, the inner layer is a loose layer, the pore volume ratio of the loose layer is 5-99%, and the pore diameter is 1-200 nm; the outer layer is a compact layer, the pore volume of the compact layer accounts for 0.001-80%, the pore volume of the compact layer is smaller than the pore volume of the loose layer, and the pore diameter is 1-200 nm; the total diameter of the inner layer and the outer layer is 8.0-30.0 mu m.
The second object of the invention is to provide a preparation method of the nickel cobalt manganese hydroxide with narrow distribution and large particles, which can prepare the precursor with narrow particle size distribution, and adopts low temperature, low pH and low raw material flow to obtain seed crystals with proper quantity and larger particle size, and greatly promotes the raw material flow to enable the seed crystals to grow fast, form a loose porous inner layer, control the reaction time and inhibit the cracking of particles; the temperature, the pH value and the stirring power per unit volume are gradually reduced, the generation of small particles is restrained, the porosity is controlled through oxidation, the phenomenon that primary particles are excessively densely and smoothly stacked due to high solid content is avoided, and the compact outer layer containing a small amount of pores is obtained. The precursor is provided with an inner loose layer with more pores and an outer compact layer with less pores, so that the prepared positive electrode active material has the advantages that on one hand, certain high compactness is kept, higher structural stability is ensured, side reactions of electrolyte on the surface of the material are reduced, gas production is effectively inhibited, and the cycle performance of the positive electrode active material is improved; on the other hand, the pore structure of the positive electrode active material is beneficial to the intercalation and deintercalation of lithium, and ensures the higher capacity and the higher rate performance of the positive electrode active material; meanwhile, the special internal loose layer can effectively buffer the volume change of the positive electrode active material in the charge and discharge process, inhibit the problems of particle cracking and the like caused by volume expansion, and further improve the cycle performance.
Therefore, the invention adopts the following technical scheme: the preparation method of the narrow-distribution large-particle nickel cobalt manganese hydroxide comprises the following steps:
Step 1, according to the required molar ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely x: y: z, selecting nickel, cobalt and manganese soluble salts as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 1.2-2.7 mol/L, preparing a sodium hydroxide solution with the concentration of 1.0-13.0 mol/L, and preparing ammonia water with the concentration of 1.0-12.0 mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process;
Step 4, adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water prepared in the step 1 into a reaction kettle in parallel under continuous stirring to react, and controlling the stirring speed, the reaction temperature, the pH and the ammonia concentration to form seed crystals in the reaction kettle;
step 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH, continuously controlling the reaction temperature and the ammonia concentration, gradually increasing the flow of the mixed metal salt solution, and then keeping the flow of the mixed metal salt solution stable;
Step 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and starting to continuously introduce oxidizing gas;
step 7, after the solid content in the reaction kettle reaches a target value, gradually reducing the temperature, the pH and the stirring power per unit volume, keeping stable, and continuously controlling the ammonia concentration;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.
Further, the pH value of the reaction starting-up base solution in the step 3 at 45 ℃ is 11.2-12.5, and the ammonia concentration is 1.0-10.0 g/L.
Further, in the step 4, the adding amount of the added mixed metal salt solution per hour is 0.001-0.02 of the total volume of the reaction kettle, the stirring power per unit volume is 3-20W/L, the reaction temperature is controlled to be 50.0-70.0 ℃, the pH value at 45 ℃ is controlled to be 11.2-12.5, and the ammonia concentration is controlled to be 1.0-10.0 g/L.
In step 5, the addition amount per hour is controlled to be 0.01-0.1 of the total volume of the reaction kettle when the flow rate of the mixed metal salt solution is stable, the flow rate of the mixed metal salt solution is improved for 1-100 h, the reaction temperature is controlled to be 50.0-70.0 ℃, the pH at 45 ℃ is controlled to be 10.8-11.3, and the ammonia concentration is controlled to be 1.0-10.0 g/L.
In step 6, the oxidizing gas is air or oxygen, and the ratio of the introduced amount to the nitrogen is 0.01-100:1.
Further, in the step 7, the target value of the solid content is 50 to 500g/L, the temperature in the stable stage is maintained at 40.0 to 65.0 ℃, the pH at 45 ℃ is 10.4 to 10.9, the stirring power per unit volume is 0.001 to 3W/L, and the ammonia concentration is 1.0 to 10.0g/L.
The invention has the following beneficial effects: the nickel cobalt manganese oxide positive electrode active material prepared by taking the nickel cobalt manganese oxide positive electrode active material as a precursor has the characteristic of compact outer layer, ensures higher structural stability by high compactness of a compact region, reduces side reaction of electrolyte on the surface of the positive electrode active material by the compact region at the outermost part, and effectively inhibits gas production, thereby improving the cycle performance of the positive electrode active material; in addition, the pore structure of the positive electrode active material is beneficial to the intercalation and deintercalation of lithium, and ensures the higher capacity and the higher rate performance of the positive electrode active material; meanwhile, the special internal loose layer can effectively buffer the volume change of the positive electrode active material in the charge and discharge process, inhibit the problems of particle cracking and the like caused by volume expansion, and further improve the cycle performance.
The preparation method of the narrow-distribution large-particle nickel cobalt manganese hydroxide is characterized in that large seed crystals are obtained through low temperature, low pH and low raw material flow in the initial stage of synthesis, the seed crystal quantity can be effectively controlled, the regulation and control of the seed crystal quantity according to actual needs are realized, and the problems of slow growth caused by excessive seed crystals in the process of synthesizing large particles, complicated operation and material waste caused by the need of turning out or discharging are effectively avoided; after nucleation is finished, the flow rate of the mixed metal salt solution is immediately and rapidly increased, so that the mixed metal salt solution rapidly grows, the synthesis productivity is improved, an internal porous loose structure can be formed, and in addition, the internal loose structure can be further regulated and controlled in a mode of improving the flow rate of raw materials; in the middle and later stages of synthesis, the synthesis temperature, pH and stirring power per unit volume are reduced linearly or nonlinearly, so that three parameters are maintained at lower level, small particles are effectively avoided, and large nickel cobalt manganese hydroxide particles with concentrated particle size distribution are obtained under high solid content; meanwhile, in the synthesis process, a proper amount of oxidizing gas is introduced to loosen the arrangement of particles, so that the primary particles are excessively tightly stacked after the solid content is restrained from being increased, and the growth speed is increased; according to the method, after the solid content is increased, the surface of particles is excessively collided and too smooth in the synthesis process, so that newly formed crystal nuclei are difficult to accumulate and grow.
The product of the invention can be widely applied to the sintering production of the lithium battery anode material, in particular to the sintering production of the ternary lithium battery anode material; the method of the invention can be widely applied to the production process of nickel cobalt manganese hydroxide.
Drawings
FIG. 1 is a 1000-fold FESEM image of a narrow-distribution large-particle nickel cobalt manganese hydroxide prepared according to example 1 of the present invention;
FIG. 2 is a 5000-fold FESEM image of a narrow-distribution large-particle nickel cobalt manganese hydroxide prepared according to example 1 of the present invention;
FIG. 3 is a 10000-fold FESEM image of a cross section of a narrow-distribution large-particle nickel cobalt manganese hydroxide prepared in example 1 of the present invention;
FIG. 4 is a 10000-fold FESEM image of a cross section of a narrow-distribution large-particle nickel cobalt manganese hydroxide prepared in example 2 of the present invention.
Detailed Description
The following examples will enable those skilled in the art to more fully understand the present invention and are not intended to limit the same in any way.
Example 1
A narrow distribution large particle nickel cobalt manganese hydroxide represented by the general formula Ni 0.5Co0.2Mn0.3(OH)2; the nickel cobalt manganese hydroxide is measured to be similar spherical particles in microscopic morphology by a scanning electron microscope, and the D50 is measured to be 10.4 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3 by a laser particle size analysis diffraction method, and the particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50. The inside of the particles showed radial growth, and the section taken by the argon ion beam cutting off the particles showed that the particles showed a loose porous internal structure. The primary particles are in a strip shape with clear textures, the length of the strip is 80-500 nm, and the width of the strip is 30-250 nm. The particles are divided into an inner layer and an outer layer, the inner layer is loose and has more pores, and the diameter is 2.0-2.5 mu m; the outer layer is compact, the pores are less, and the diameter is 10.0-10.5 mu m.
The preparation method of the narrow-distribution large-particle nickel cobalt manganese hydroxide comprises the following steps:
Step 1, according to the required mole ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely 5:2:3, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 13.0mol/L, and preparing ammonia water with the concentration of 12.0mol/L as a complexing agent.
And 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle.
Step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process; the pH value of the starting base solution is 12.5 (45 ℃) and the ammonia concentration is 10.0g/L.
And 4, adding the mixed metal salt solution prepared in the step 1, the sodium hydroxide solution and the ammonia water into a reaction kettle in parallel under continuous stirring to react, wherein the adding amount of the added mixed metal salt solution per hour is 0.02 of the total volume of the reaction kettle, the stirring power per unit volume is controlled to be 20W/L, the reaction temperature is controlled to be 70.0 ℃, the pH value is controlled to be 12.5 (45 ℃), and the ammonia concentration is controlled to be 10.0g/L.
And 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH to 11.3 (45 ℃), continuously controlling the reaction temperature to 70.0 ℃ and the ammonia concentration to 10.0g/L, gradually increasing the flow of the mixed metal salt solution to 0.1 of the total volume of the reaction kettle in a linear manner within 100h, and then keeping the flow of the mixed metal salt solution stable.
And 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and continuously introducing air or oxygen, wherein the ratio of the introduced amount to the nitrogen is 100:1.
Step 7, after the solid content in the reaction kettle reaches 500g/L, gradually reducing the temperature to 50.0 ℃ and the pH to 10.9 (45 ℃) in a linear mode, keeping the stirring power per unit volume to be 0.01W/L, and continuously controlling the ammonia concentration to be 10.0g/L;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.
Example 2
A narrow distribution large particle nickel cobalt manganese hydroxide represented by the general formula Ni 0.6Co0.2Mn0.2(OH)2; the nickel cobalt manganese hydroxide is measured to be similar spherical particles in microscopic morphology by a scanning electron microscope, and the D50 is measured to be 9.6 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3 by a laser particle size analysis diffraction method, and the particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50. The inside of the particles showed radial growth, and the section taken by the argon ion beam cutting off the particles showed that the particles showed a loose porous internal structure. The primary particles are in a strip shape with clear textures, the length of the strip is 80-500 nm, and the width of the strip is 30-250 nm. The particles are divided into an inner layer and an outer layer, the inner layer is loose and has more pores, and the diameter is 1.8-2.1 mu m; the outer layer is compact, the pores are less, and the diameter is 9.3-9.8 mu m.
The preparation method comprises the following steps:
Step 1, according to the required mole ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely 6:2:2, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 7.0mol/L, preparing a sodium hydroxide solution with the concentration of 6.0mol/L, and preparing ammonia water as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process; the pH value of the starting base solution is 11.9 (45 ℃), and the ammonia concentration is 5.0g/L;
Step 4, adding the mixed metal salt solution prepared in the step 1, sodium hydroxide solution and ammonia water into a reaction kettle in parallel under continuous stirring to react, wherein the adding amount of the added mixed metal salt solution per hour is 0.01 of the total volume of the reaction kettle, the stirring power per unit volume is controlled to be 10W/L, the reaction temperature is controlled to be 60.0 ℃, the pH value is controlled to be 11.9 (45 ℃), and the ammonia concentration is controlled to be 5.0g/L;
step 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH to 11.0 (45 ℃), continuously controlling the reaction temperature to 60.0 ℃ and the ammonia concentration to 5.0g/L, gradually increasing the flow of the mixed metal salt solution to 0.05 of the total volume of the reaction kettle within 50 hours in a linear mode, and then keeping the flow of the mixed metal salt solution stable;
And 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and continuously introducing air or oxygen, wherein the ratio of the introduced amount to the nitrogen is 50:1.
Step 7, after the solid content in the reaction kettle reaches 250g/L, gradually reducing the temperature to 45.0 ℃ and the pH to 10.6 (45 ℃) in a linear mode, keeping the stirring power per unit volume to be 0.5W/L, and continuously controlling the ammonia concentration to be 5.0g/L;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.
Example 3
A narrow distribution large particle nickel cobalt manganese hydroxide represented by the general formula Ni 0.8Co0.1Mn0.1(OH)2; the nickel cobalt manganese hydroxide is measured to be similar spherical particles in microscopic morphology by a scanning electron microscope, and the D50 is measured to be 10.6 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3 by a laser particle size analysis diffraction method, and the particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50. The inside of the particles showed radial growth, and the section taken by the argon ion beam cutting off the particles showed that the particles showed a loose porous internal structure. The primary particles are in a strip shape with clear textures, the length of the strip is 80-500 nm, and the width of the strip is 30-250 nm. The particles are divided into an inner layer and an outer layer, the inner layer is loose and has more pores, and the diameter is 3.0-3.5 mu m; the outer layer is compact, the pores are less, and the diameter is 10.0-11.0 mu m. The preparation method comprises the following steps:
step 1, according to the required mole ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely 8:1:1, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 1.2mol/L, preparing a sodium hydroxide solution with the concentration of 1.0mol/L, and preparing ammonia water with the concentration of 1.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process; the pH value of the starting base solution is 11.2 (45 ℃), and the ammonia concentration is 1.0g/L;
step 4, adding the mixed metal salt solution prepared in the step 1, sodium hydroxide solution and ammonia water into a reaction kettle in parallel under continuous stirring to react, wherein the adding amount of the added mixed metal salt solution per hour is 0.001 of the total volume of the reaction kettle, the stirring power per unit volume is controlled to be 20W/L, the reaction temperature is controlled to be 50.0 ℃, the pH value is controlled to be 11.2 (45 ℃), and the ammonia concentration is controlled to be 1.0g/L;
step 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH to 10.8 (45 ℃), continuously controlling the reaction temperature to 50.0 ℃ and the ammonia concentration to 1.0g/L, gradually increasing the flow of the mixed metal salt solution to 0.01 of the total volume of the reaction kettle in a linear manner within 1h, and then keeping the flow of the mixed metal salt solution stable;
And 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and continuously introducing air or oxygen, wherein the ratio of the introduced amount to the nitrogen is 0.01:1.
Step 7, after the solid content in the reaction kettle reaches 50g/L, gradually reducing the temperature to 40.0 ℃ and the pH to 10.4 (45 ℃) in a linear mode, keeping the stirring power per unit volume to be 0.001W/L, and continuously controlling the ammonia concentration to be 1.0g/L;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.
Example 4
A narrow distribution large particle nickel cobalt manganese hydroxide represented by the general formula Ni 0.6Co0.2Mn0.2(OH)2; the nickel cobalt manganese hydroxide is measured to be similar spherical particles in microscopic morphology by a scanning electron microscope, and the D50 is measured to be 10.4 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3 by a laser particle size analysis diffraction method, and the particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50. The inside of the particles showed radial growth, and the section taken by the argon ion beam cutting off the particles showed that the particles showed a loose porous internal structure. The primary particles are in a strip shape with clear textures, the length of the strip is 80-500 nm, and the width of the strip is 30-250 nm. The particles are divided into an inner layer and an outer layer, the inner layer is loose and has more pores, and the diameter is 2.0-2.5 mu m; the outer layer is compact, the pores are less, and the diameter is 10.0-11.0 mu m. The preparation method comprises the following steps:
Step 1, according to the required mole ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely 6:2:2, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 2.7mol/L, preparing a sodium hydroxide solution with the concentration of 13.0mol/L, and preparing ammonia water with the concentration of 12.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
Step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process; the pH value of the starting base solution is 12.5 (45 ℃), and the ammonia concentration is 10.0g/L;
Step 4, adding the mixed metal salt solution prepared in the step 1, sodium hydroxide solution and ammonia water into a reaction kettle in parallel under continuous stirring to react, wherein the adding amount of the added mixed metal salt solution per hour is 0.02 of the total volume of the reaction kettle, the stirring power per unit volume is controlled to be 10W/L, the reaction temperature is controlled to be 70.0 ℃, the pH value is controlled to be 12.5 (45 ℃), and the ammonia concentration is controlled to be 10.0g/L;
Step 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH to 11.3 (45 ℃), continuously controlling the reaction temperature to 70.0 ℃ and the ammonia concentration to 10.0g/L, gradually increasing the flow of the mixed metal salt solution to 0.1 of the total volume of the reaction kettle within 100 hours in a linear mode, and then keeping the flow of the mixed metal salt solution stable;
and 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and continuously introducing air or oxygen, wherein the ratio of the introduced amount to the nitrogen is 100:1.
Step 7, after the solid content in the reaction kettle reaches 500g/L, gradually reducing the temperature to 65.0 ℃ and the pH to 10.9 (45 ℃) in a linear mode, keeping the stirring power per unit volume to be 1W/L, and continuously controlling the ammonia concentration to be 10.0g/L;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.
Example 5
A narrow distribution large particle nickel cobalt manganese hydroxide represented by the general formula Ni 0.8Co0.1Mn0.1(OH)2; the nickel cobalt manganese hydroxide is measured to be similar spherical particles in microscopic morphology by a scanning electron microscope, and the D50 is measured to be 9.6 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3 by a laser particle size analysis diffraction method, and the particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50. The inside of the particles showed radial growth, and the section taken by the argon ion beam cutting off the particles showed that the particles showed a loose porous internal structure. The primary particles are in a strip shape with clear textures, the length of the strip is 80-500 nm, and the width of the strip is 30-250 nm. The particles are divided into an inner layer and an outer layer, the inner layer is loose and has more pores, and the diameter is 1.8-2.1 mu m; the outer layer is compact, the pores are less, and the diameter is 9.3-9.8 mu m.
The preparation method comprises the following steps:
Step 1, according to the required mole ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely 8:1:1, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 2.0mol/L, preparing a sodium hydroxide solution with the concentration of 7.0mol/L, and preparing ammonia water with the concentration of 6.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process; the pH value of the starting base solution is 11.9 (45 ℃), and the ammonia concentration is 5.0g/L;
step 4, adding the mixed metal salt solution prepared in the step 1, sodium hydroxide solution and ammonia water into a reaction kettle in parallel under continuous stirring to react, wherein the adding amount of the added mixed metal salt solution per hour is 0.01 of the total volume of the reaction kettle, the stirring power per unit volume is controlled to be 5W/L, the reaction temperature is controlled to be 60.0 ℃, the pH value is controlled to be 11.9 (45 ℃), and the ammonia concentration is controlled to be 5.0g/L;
step 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH to 11.0 (45 ℃), continuously controlling the reaction temperature to 60.0 ℃ and the ammonia concentration to 5.0g/L, gradually increasing the flow of the mixed metal salt solution to 0.05 of the total volume of the reaction kettle within 50 hours in a linear mode, and then keeping the flow of the mixed metal salt solution stable;
And 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and continuously introducing air or oxygen, wherein the ratio of the introduced amount to the nitrogen is 50:1.
Step 7, after the solid content in the reaction kettle reaches 250g/L, gradually reducing the temperature to 55.0 ℃ and the pH to 10.7 (45 ℃) in a linear mode, keeping the stirring power per unit volume to be 0.001W/L, and continuously controlling the ammonia concentration to be 5.0g/L;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.
Example 6
A narrow distribution large particle nickel cobalt manganese hydroxide represented by the general formula Ni 0.7Co0.1Mn0.2(OH)2; the nickel cobalt manganese hydroxide is measured to be similar spherical particles in microscopic morphology by a scanning electron microscope, and the D50 is measured to be 10.6 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3 by a laser particle size analysis diffraction method, and the particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50. The inside of the particles showed radial growth, and the section taken by the argon ion beam cutting off the particles showed that the particles showed a loose porous internal structure. The primary particles are in a strip shape with clear textures, the length of the strip is 80-500 nm, and the width of the strip is 30-250 nm. The particles are divided into an inner layer and an outer layer, the inner layer is loose and has more pores, and the diameter is 3.0-3.5 mu m; the outer layer is compact, the pores are less, and the diameter is 10.0-11.0 mu m. The preparation method comprises the following steps:
Step 1, according to the required mole ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely 7:1:2, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 1.2mol/L, preparing a sodium hydroxide solution with the concentration of 1.0mol/L, and preparing ammonia water with the concentration of 1.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process; the pH value of the starting base solution is 11.2 (45 ℃), and the ammonia concentration is 1.0g/L;
step 4, adding the mixed metal salt solution prepared in the step 1, sodium hydroxide solution and ammonia water into a reaction kettle in parallel under continuous stirring to react, wherein the adding amount of the added mixed metal salt solution per hour is 0.001 of the total volume of the reaction kettle, the stirring power per unit volume is controlled to be 3W/L, the reaction temperature is controlled to be 50.0 ℃, the pH value is controlled to be 11.2 (45 ℃), and the ammonia concentration is controlled to be 1.0g/L;
step 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH to 10.8 (45 ℃), continuously controlling the reaction temperature to 50.0 ℃ and the ammonia concentration to 1.0g/L, gradually increasing the flow of the mixed metal salt solution to 0.01 of the total volume of the reaction kettle in a linear manner within 1h, and then keeping the flow of the mixed metal salt solution stable;
And 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and continuously introducing air or oxygen, wherein the ratio of the introduced amount to the nitrogen is 0.01:1.
Step 7, after the solid content in the reaction kettle reaches 50g/L, gradually reducing the temperature to 40.0 ℃ and the pH to 10.4 (45 ℃) in a linear mode, keeping the stirring power per unit volume to be 0.001W/L, and continuously controlling the ammonia concentration to be 1.0g/L;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.
Example 7
A narrow distribution large particle nickel cobalt manganese hydroxide represented by the general formula Ni 0.4Co0.4Mn0.2(OH)2; the nickel cobalt manganese hydroxide is measured to be similar spherical particles in microscopic morphology by a scanning electron microscope, and the D50 is measured to be 10.6 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3 by a laser particle size analysis diffraction method, and the particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50. The inside of the particles showed radial growth, and the section taken by the argon ion beam cutting off the particles showed that the particles showed a loose porous internal structure. The primary particles are in a strip shape with clear textures, the length of the strip is 80-500 nm, and the width of the strip is 30-250 nm. The particles are divided into an inner layer and an outer layer, the inner layer is loose and has more pores, and the diameter is 2.0-2.5 mu m; the outer layer is compact, the pores are less, and the diameter is 10.0-11.0 mu m. The preparation method comprises the following steps:
Step 1, according to the required mole ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely 4:4:2, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 2.7mol/L, preparing a sodium hydroxide solution with the concentration of 13.0mol/L, and preparing ammonia water with the concentration of 12.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
Step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process; the pH value of the starting base solution is 12.5 (45 ℃), and the ammonia concentration is 10.0g/L;
step 4, adding the mixed metal salt solution prepared in the step 1, sodium hydroxide solution and ammonia water into a reaction kettle in parallel under continuous stirring to react, wherein the adding amount of the added mixed metal salt solution per hour is 0.02 of the total volume of the reaction kettle, the stirring power per unit volume is controlled to be 20W/L, the reaction temperature is controlled to be 70.0 ℃, the pH value is controlled to be 12.5 (45 ℃), and the ammonia concentration is controlled to be 10.0g/L;
Step 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH to 11.3 (45 ℃), continuously controlling the reaction temperature to 70.0 ℃ and the ammonia concentration to 10.0g/L, gradually increasing the flow of the mixed metal salt solution to 0.1 of the total volume of the reaction kettle within 100 hours in a linear mode, and then keeping the flow of the mixed metal salt solution stable;
and 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and continuously introducing air or oxygen, wherein the ratio of the introduced amount to the nitrogen is 100:1.
Step 7, after the solid content in the reaction kettle reaches 500g/L, gradually reducing the temperature to 65.0 ℃ and the pH to 10.9 (45 ℃) in a linear mode, keeping the stirring power per unit volume to 3W/L, and continuously controlling the ammonia concentration to 10.0g/L;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.
Example 8
A narrow distribution large particle nickel cobalt manganese hydroxide represented by the general formula Ni 0.6Co0.2Mn0.2(OH)2; the nickel cobalt manganese hydroxide is measured to be similar spherical particles in microscopic morphology by a scanning electron microscope, and the D50 is measured to be 11.5 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3 by a laser particle size analysis diffraction method, and the particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50. The inside of the particles showed radial growth, and the section taken by the argon ion beam cutting off the particles showed that the particles showed a loose porous internal structure. The primary particles are in a strip shape with clear textures, the length of the strip is 80-500 nm, and the width of the strip is 30-250 nm. The particles are divided into an inner layer and an outer layer, the inner layer is loose and has more pores, and the diameter is 1.8-2.1 mu m; the outer layer is compact, the pores are less, and the diameter is 11.3-11.8 mu m. The preparation method comprises the following steps:
Step 1, according to the required mole ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely 6:2:2, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 7.0mol/L, preparing a sodium hydroxide solution with the concentration of 6.0mol/L, and preparing ammonia water as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process; the pH value of the starting base solution is 11.9 (45 ℃), and the ammonia concentration is 5.0g/L;
Step 4, adding the mixed metal salt solution prepared in the step 1, sodium hydroxide solution and ammonia water into a reaction kettle in parallel under continuous stirring to react, wherein the adding amount of the added mixed metal salt solution per hour is 0.01 of the total volume of the reaction kettle, the stirring power per unit volume is controlled to be 12W/L, the reaction temperature is controlled to be 60.0 ℃, the pH value is controlled to be 11.9 (45 ℃), and the ammonia concentration is controlled to be 5.0g/L;
step 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH to 11.0 (45 ℃), continuously controlling the reaction temperature to 60.0 ℃ and the ammonia concentration to 5.0g/L, gradually increasing the flow of the mixed metal salt solution to 0.05 of the total volume of the reaction kettle within 50 hours in a linear mode, and then keeping the flow of the mixed metal salt solution stable;
And 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and continuously introducing air or oxygen, wherein the ratio of the introduced amount to the nitrogen is 50:1.
Step 7, after the solid content in the reaction kettle reaches 250g/L, gradually reducing the temperature to 55.0 ℃ and the pH to 10.7 (45 ℃) in a linear mode, keeping the stirring power per unit volume to be 1.5W/L, and continuously controlling the ammonia concentration to be 5.0g/L;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.
Example 9
A narrow distribution large particle nickel cobalt manganese hydroxide represented by the general formula Ni 0.9Co0.05Mn0.05(OH)2; the nickel cobalt manganese hydroxide is measured to be similar spherical particles in microscopic morphology by a scanning electron microscope, and the D50 is measured to be 10.6 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3 by a laser particle size analysis diffraction method, and the particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50. The inside of the particles showed radial growth, and the section taken by the argon ion beam cutting off the particles showed that the particles showed a loose porous internal structure. The primary particles are in a strip shape with clear textures, the length of the strip is 80-500 nm, and the width of the strip is 30-250 nm. The particles are divided into an inner layer and an outer layer, the inner layer is loose and has more pores, and the diameter is 3.0-3.5 mu m; the outer layer is compact, the pores are less, and the diameter is 10.0-11.0 mu m. The preparation method comprises the following steps:
step 1, according to the required mole ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely 9:0.5:0.5, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 1.2mol/L, preparing a sodium hydroxide solution with the concentration of 1.0mol/L, and preparing ammonia water with the concentration of 1.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process; the pH value of the starting base solution is 11.2 (45 ℃), and the ammonia concentration is 1.0g/L;
Step 4, adding the mixed metal salt solution prepared in the step 1, sodium hydroxide solution and ammonia water into a reaction kettle in parallel under continuous stirring to react, wherein the adding amount of the added mixed metal salt solution per hour is 0.001 of the total volume of the reaction kettle, the stirring power per unit volume is controlled to be 10W/L, the reaction temperature is controlled to be 50.0 ℃, the pH value is controlled to be 11.2 (45 ℃), and the ammonia concentration is controlled to be 1.0g/L;
step 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH to 10.8 (45 ℃), continuously controlling the reaction temperature to 50.0 ℃ and the ammonia concentration to 1.0g/L, gradually increasing the flow of the mixed metal salt solution to 0.01 of the total volume of the reaction kettle in a linear manner within 1h, and then keeping the flow of the mixed metal salt solution stable;
And 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and continuously introducing air or oxygen, wherein the ratio of the introduced amount to the nitrogen is 0.01:1.
Step 7, after the solid content in the reaction kettle reaches 50g/L, gradually reducing the temperature to 40.0 ℃ and the pH to 10.4 (45 ℃) in a linear mode, keeping the stirring power per unit volume to be 0.2W/L, and continuously controlling the ammonia concentration to be 1.0g/L;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.

Claims (9)

1. The nickel cobalt manganese hydroxide is characterized by being represented by a general formula Ni xCoyMnz(OH)2, wherein x+y+z=1, the values of x, y and z are all 0-1, and x, y and z are all not equal to 0 and 1; the nickel cobalt manganese hydroxide is measured to be similar spherical particles in microscopic morphology by a scanning electron microscope, D50 is measured to be 8.0-20.0 mu m, dmin is more than 5.0 mu m, dmax is less than 30 mu m, dmax/Dmin is less than 3, and particle size distribution diameter distance K90= (D90-D10)/D50 is less than or equal to 0.50 by a laser particle size analysis diffraction method;
the nickel cobalt manganese hydroxide particles are divided into an inner layer and an outer layer, the diameter of the inner layer is 1.0-8.0 mu m, the inner layer is a loose layer, the pore volume of the loose layer accounts for 5-99%, and the pore diameter is 1-200 nm; the outer layer is a compact layer, the pore volume of the compact layer accounts for 0.001-80%, the pore volume of the compact layer is smaller than the pore volume of the loose layer, and the pore diameter is 1-200 nm; the total diameter of the inner layer and the outer layer is 8.0-30.0 mu m.
2. A narrow distribution large particle nickel cobalt manganese hydroxide according to claim 1, wherein the interior of the nickel cobalt manganese hydroxide particles is in a radial form, and a cross section taken through the argon ion beam cutoff particles shows that the particles exhibit a porous internal structure.
3. The narrow-distribution large-particle nickel cobalt manganese hydroxide according to claim 1, wherein the primary particles of the nickel cobalt manganese hydroxide are in the shape of clear-textured 'slivers', the 'slivers' are 80-500 nm in length and 30-250 nm in width.
4. A process for preparing a narrow distribution large particle nickel cobalt manganese hydroxide according to any one of claims 1 to 3, comprising the steps of:
Step 1, according to the required molar ratio of nickel, cobalt and manganese elements in the nickel cobalt manganese hydroxide, namely x: y: z, selecting nickel, cobalt and manganese soluble salts as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 1.2-2.7 mol/L, preparing a sodium hydroxide solution with the concentration of 1.0-13.0 mol/L, and preparing ammonia water with the concentration of 1.0-12.0 mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution, and keeping a nitrogen gas inlet state in the synthesis process;
step 4, adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water prepared in the step 1 into a reaction kettle in parallel under continuous stirring to react, controlling the stirring speed, the reaction temperature, the pH value and the ammonia concentration, wherein the pH value at 45 ℃ is 11.2-12.5, and forming seed crystals in the reaction kettle;
step 5, when the seed crystal amount in the reaction kettle reaches the target requirement, reducing the reaction pH to 10.8-11.3 at 45 ℃, continuously controlling the reaction temperature and the ammonia concentration, gradually increasing the flow of the mixed metal salt solution, and then keeping the flow of the mixed metal salt solution stable;
Step 6, starting a thickener to start to clear after the liquid level reaches the clear requirement, maintaining the liquid level in the reaction kettle to be stable, gradually increasing the solid content in the reaction kettle, and starting to continuously introduce oxidizing gas;
step 7, after the solid content in the reaction kettle reaches a target value, gradually reducing the temperature, the pH and the stirring power per unit volume, keeping stable, and continuously controlling the ammonia concentration;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sieving and demagnetizing sequentially to obtain the large-particle nickel-cobalt-manganese hydroxide.
5. The method according to claim 4, wherein the pH of the reaction starting-up base solution in step 3 at 45℃is 11.2-12.5 and the ammonia concentration is 1.0-10.0 g/L.
6. The method according to claim 4, wherein in the step 4, the added mixed metal salt solution is added in an amount of 0.001-0.02 per hour based on the total volume of the reaction vessel, the stirring power per unit volume is 3-20W/L, the reaction temperature is controlled to be 50.0-70.0 ℃, and the ammonia concentration is controlled to be 1.0-10.0 g/L.
7. The method according to claim 4, wherein in the step 5, the amount of the mixed metal salt solution added per hour is controlled to be 0.01-0.1 of the total volume of the reaction vessel when the flow rate of the mixed metal salt solution is stabilized, the time for increasing the flow rate of the mixed metal salt solution is 1-100 hours, the reaction temperature is controlled to be 50.0-70.0 ℃, and the ammonia concentration is controlled to be 1.0-10.0 g/L.
8. The method according to claim 4, wherein in the step 6, the oxidizing gas is air or oxygen, and the ratio of the amount of the oxidizing gas to the amount of the nitrogen is 0.01-100:1.
9. The method according to claim 4, wherein in the step 7, the target value of the solid content is 50 to 500g/L, the temperature in the steady state is maintained at 40.0 to 65.0 ℃, the pH at 45 ℃ is 10.4 to 10.9, the stirring power per unit volume is 0.001 to 3W/L, and the ammonia concentration is 1.0 to 10.0g/L.
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