CN111204821A - Nickel-cobalt-manganese hydroxide with particle size in bimodal distribution and preparation method thereof - Google Patents

Nickel-cobalt-manganese hydroxide with particle size in bimodal distribution and preparation method thereof Download PDF

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CN111204821A
CN111204821A CN202010109292.8A CN202010109292A CN111204821A CN 111204821 A CN111204821 A CN 111204821A CN 202010109292 A CN202010109292 A CN 202010109292A CN 111204821 A CN111204821 A CN 111204821A
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particle size
cobalt
nickel
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reaction
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王宏刚
王娟
邱天
高炯信
沈震雷
周勤俭
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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 relates to a nickel-cobalt-manganese hydroxide with bimodal distribution of particle size, wherein the nickel-cobalt-manganese hydroxide with bimodal distribution of particle size is determined to be spheroidal particles in microscopic morphology by an analytical scanning electron microscope method; determining that the particle size distribution diagram is bimodal through a particle size analysis laser diffraction method, wherein bimodal peak positions are respectively located within 3-6 microns and 8-15 microns, and the height ratio of the bimodal peak values is 0.25-4; the nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution has two different particle size distributions, higher tap density, no agglomeration of small particles, and better sphericity, and is used for improving the problems of poor volume specific capacity, poor cycle performance and poor rate capability of a nickel-cobalt-manganese-based oxide anode material synthesized subsequently.

Description

Nickel-cobalt-manganese hydroxide with particle size in bimodal distribution 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 nickel-cobalt-manganese hydroxide with particle size in bimodal distribution and a preparation method thereof.
Background
As a novel green power source, the lithium ion battery has been widely applied to the fields of 3C digital electronic products, electric tools, electric vehicles, energy storage, and the like. One of the key factors determining the electrochemical performance of lithium ion batteries is the positive electrode material. Currently, some commonly used cathode materials include lithium manganate, lithium cobaltate, lithium iron phosphate, lithium nickel cobalt manganese, and the like. Due to the obvious synergistic effect among Ni, Co and Mn, the performance of NMC is better than that of a single-component layered cathode material, and the NMC is considered to be one of the most promising novel cathode materials. The ternary anode material has good comprehensive performance and becomes the main anode material in the market.
The nickel cobalt manganese hydroxide, namely the nickel cobalt manganese ternary precursor, is added with a lithium source and is sintered at high temperature to synthesize the nickel cobalt lithium manganate. The size, the morphology, the structure and the like of the ternary precursor have direct influence on the technical indexes of the nickel cobalt lithium manganate, so that the precursor is very important for the production of ternary materials.
In the field of the existing vehicle power battery, a mode of mixing large and small particles is adopted to improve the compaction density of a product, and higher capacity is obtained in a limited volume space. The current mainstream process is to mix the large and small particles after separate sintering. However, the separate sintering and blending have the following problems:
(1) different production processes are required to be designed for the preparation and subsequent sintering of the precursors of the large and small particles, so that the production cost is greatly increased;
(2) the problems of secondary spherical particle agglomeration and poor sphericity exist during the preparation of the precursor with small particle size;
(3) when the small-particle-size precursor secondary spherical particles are synthesized, good crystal seeds are difficult to obtain, so that the density is low;
(4) the tap density of the whole is low, and the tap density of the precursors of the large and small particles is difficult to break through 2.2g/cm high-speed thin-wall high-speed thin-.
Disclosure of Invention
The invention provides a nickel-cobalt-manganese hydroxide with bimodal distribution of particle size as a precursor of an active substance of a nickel-cobalt-manganese lithium battery anode material, wherein the precursor has two different particle size distributions, has higher tap density, has no agglomeration phenomenon of small particles and better sphericity, and is used for improving the problems of poor volume specific capacity, poor cycle performance and poor rate capability of a nickel-cobalt-manganese-based oxide anode material synthesized subsequently.
The technical scheme adopted by the invention is as follows: the nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution is characterized in that the micro-morphology of the nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution is determined to be spheroidal particles by an analytical scanning electron microscope method; the particle size distribution graph is determined to be bimodal through a particle size analysis laser diffraction method, the bimodal peak positions are respectively located within 3-6 microns and 8-15 microns, and the height ratio of the bimodal peak values is 0.25-4.
The sphericity index phi of the nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution is 1.0-1.6, wherein phi = Di/Dc, Di is the maximum inscribed sphere radius of the particles, Dc is the minimum inscribed sphere radius of the same particles, and the closer phi is to 1, the better the sphericity of the particles is.
The nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution is prepared from the general formula NixCoyMnz(OH)2Wherein 0.30. ltoreq. x.ltoreq.0.92, 0. ltoreq. y.ltoreq.0.50, 0. ltoreq. z.ltoreq.0.50, and x + y + z = 1.
The nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution is determined by a tap density meter to have the tap density of more than or equal to 2.3g/cm3。
The invention provides a preparation method of nickel-cobalt-manganese hydroxide with particle size in bimodal distribution, which is realized by the following steps:
step 1, according to the molar ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide with the required particle size in bimodal distribution, namely x: y: z, selecting soluble salts of nickel, cobalt and manganese as raw materials;
step 2, preparing the nickel, cobalt and manganese soluble salts selected in the step 1 and pure water into a mixed salt solution with the total metal ion concentration of 1.2-2.7 mol/L;
step 3, preparing a sodium hydroxide solution with the concentration of 3.0-12.0 mol/L;
step 4, preparing ammonia water with the mass concentration of 5-30% as a complexing agent;
step 5, opening a jacket of the reaction kettle for water inlet and water return, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process to prevent bivalent manganese ions from being oxidized into trivalent manganese ions;
step 6, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a base solution for starting up the reaction, wherein the base solution has higher pH and is easy to form crystal nuclei, so that preparation is made for producing larger-particle crystal nuclei;
step 7, adding the mixed metal salt solution prepared in the step 2, the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 into a reaction kettle in a concurrent flow manner for reaction, controlling the reaction temperature, the pH value and the ammonia concentration, and starting to generate larger-particle crystal nuclei in the process;
step 8, continuing feeding according to the step 7, determining the number of crystal nuclei of the larger particles according to the height ratio of the bimodal peak in the required product, reducing the reaction pH when the crystal nucleus amount of the larger particles in the reaction kettle reaches the target requirement, continuing to control the reaction temperature, the ammonia concentration and the like, and starting to grow the crystal nuclei of the larger particles; meanwhile, after the liquid level in the reaction kettle reaches the discharging requirement, starting a thickener to discharge, and maintaining the liquid level in the reaction kettle to be stable;
step 9, continuing feeding according to the step 8, when the particle size of the particles in the reaction kettle is 5-12 microns, indicating that the crystal nucleus of the larger particles grows to a certain degree, increasing the reaction pH, continuing to control the reaction temperature, the ammonia concentration and the like, and generating the crystal nucleus of the smaller particles;
step 10, continuing feeding according to the step 9, determining the number of crystal nuclei of the smaller particles according to the height ratio of the bimodal peak in the required product, reducing the reaction pH when the crystal nucleus amount of the smaller particles in the reaction kettle reaches the target requirement, continuing to control the reaction temperature, the ammonia concentration and the like, and starting to grow the crystal nuclei of the smaller particles;
step 11, continuing feeding according to the step 10, stopping feeding when the particle size of the materials in the reaction kettle is detected to meet the required requirement, namely the particle distribution is consistent with the target requirement, and continuing stirring and aging for 1-2 hours;
step 12, adding the aged slurry obtained in the step 11 into filter-pressing washing equipment for washing and filter pressing, firstly washing the slurry for 0.5 to 2 hours by using a sodium hydroxide solution with the concentration of 0.1 to 5mol/L, and washing the slurry by using pure water after filtering;
and step 13, carrying out filter pressing and dehydration on the washed material obtained in the step 12, then sending the material to a drying process, and after drying is finished, sequentially carrying out sieving and demagnetizing to obtain the nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution.
In the preparation method of the nickel-cobalt-manganese hydroxide with the particle size in the bimodal distribution, in the step 6, the pH value of the starting-up base solution is 11.2-12.4, and the ammonia concentration is 1.0-14.0 g/L.
In the preparation method of the nickel-cobalt-manganese hydroxide with the particle size in the bimodal distribution, in the step 7, the reaction temperature is controlled to be 50.0-70.0 ℃, the pH value is controlled to be 11.2-12.4, and the ammonia concentration is controlled to be 1.0-14.0 g/L.
In the preparation method of the nickel-cobalt-manganese hydroxide with the particle size in the bimodal distribution, in the step 8, the reaction pH is reduced to 10.5-11.2, the reaction temperature is controlled to be 50.0-70.0 ℃, and the ammonia concentration is 1.0-14.0 g/L.
In the preparation method of the nickel-cobalt-manganese hydroxide with the particle size in the bimodal distribution, in the step 9, the reaction pH is increased to 11.2-12.4, the reaction temperature is controlled to be 50.0-70.0 ℃, and the ammonia concentration is 1.0-14.0 g/L.
In the preparation method of the nickel-cobalt-manganese hydroxide with the particle size in the bimodal distribution, in the step 10, the reaction pH is reduced to 10.5-11.2, the reaction temperature is controlled to be 50.0-70.0 ℃, and the ammonia concentration is 1.0-14.0 g/L.
The invention has the beneficial effects that: the nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution has a proper specific surface area, less impurities and a better layered structure, and besides, the precursor has two different particle size distributions, has higher tap density, has no agglomeration phenomenon of small particles, has better sphericity, and is used for improving the problems of poor volume specific capacity, poor cycle performance and poor rate capability of a nickel-cobalt-manganese-based oxide anode material which is subsequently synthesized; the preparation method of nickel cobalt manganese hydroxide with bimodal distribution of grain size controls the quantity and size distribution of particles by regulating and controlling pH in the reaction process, meanwhile, because larger particles are preferentially produced, when smaller particles are prepared, small crystal grains are difficult to gather under the dispersion action of large particles, the phenomenon of secondary spherical particle agglomeration of a precursor with small grain size is avoided, and each small crystal grain can independently grow, so that small-grain-size particles with better sphericity and high density are obtained, the integral tap density is further improved, the volume specific capacity of a subsequently synthesized anode material is greatly improved, the safety, the cycle and the rate capability of the nickel cobalt manganese anode material are further improved, the operation is simple, and the preparation method is suitable for industrial production. 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 nickel-manganese-lithium battery anode material; the method can be widely applied to the production process of the nickel-cobalt-manganese hydroxide, and is particularly suitable for the production process of the nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution.
Drawings
FIG. 1 is a graph of particle size distribution of nickel cobalt manganese hydroxide prepared in example 1 with bimodal particle size distribution;
FIG. 2 is a 1000-fold FESEM image of nickel cobalt manganese hydroxide prepared in example 1 and having a bimodal particle size distribution;
FIG. 3 is a 3000-fold FESEM image of nickel cobalt manganese hydroxide prepared in example 1 and having a bimodal particle size distribution;
FIG. 4 is a graph of particle size distribution of nickel cobalt manganese hydroxide prepared in example 2 with bimodal particle size distribution;
FIG. 5 is a 1000-fold FESEM image of nickel cobalt manganese hydroxide prepared in example 2 and having a bimodal particle size distribution;
fig. 6 is a 3000-fold FESEM image of the nickel cobalt manganese hydroxide prepared in example 2 with a bimodal particle size distribution.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
Has a chemical formula of Ni0.6Co0.2Mn0.2(OH)2The nickel-cobalt-manganese hydroxide with bimodal distribution of particle sizes is determined to be spheroidal particles in microscopic morphology by an analytical scanning electron microscope method; the particle size distribution diagram is determined to be bimodal by a particle size analysis laser diffraction method, the bimodal peak positions are respectively positioned at 5.6 mu m and 10.5 mu m, the height ratio of the particle size distribution peak value of the smaller particles to the particle size distribution peak value of the larger particles is 0.4, the sphericity index phi of the particles is 1.0-1.6, and the tap density is determined to be more than or equal to 2.3g/cm by a tap density instrument3. The preparation method comprises the following steps:
step 1, according to the mole ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide with the required particle size in bimodal distribution, namely 6: 2: 2, selecting soluble salts of nickel, cobalt and manganese as raw materials;
step 2, preparing the nickel, cobalt and manganese soluble salts selected in the step 1 and pure water into a mixed salt solution with the total metal ion concentration of 2.05 mol/L;
step 3, preparing a sodium hydroxide solution with the concentration of 10.5 mol/L;
step 4, preparing ammonia water with the mass concentration of 9.5% as a complexing agent;
step 5, opening a jacket of the reaction kettle for water inlet and water return, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 6, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a base solution for starting up the reaction, wherein the pH value of the base solution is 11.8, and the ammonia concentration is 5.0 g/L;
step 7, adding the mixed metal salt solution prepared in the step 2, the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 into a reaction kettle in a concurrent flow manner for reaction, and controlling the reaction temperature to be 65.0 ℃, the pH to be 11.8 and the ammonia concentration to be 5.0 g/L;
step 8, continuing feeding according to the step 7, determining the number of crystal nuclei of larger particles according to the height ratio of the bimodal peak in the required product, reducing the reaction pH to 11.35 when the crystal nuclei of the larger particles in the reaction kettle reach the target requirement, controlling the reaction temperature to be 65.0 ℃ and the ammonia concentration to be 5.0 g/L; meanwhile, after the liquid level in the reaction kettle reaches the discharging requirement, starting a thickener to discharge, and maintaining the liquid level in the reaction kettle to be stable;
step 9, continuing feeding according to the step 8, when the particle size of the particles in the reaction kettle is 7.5 mu m, indicating that the crystal nucleus of larger particles grows to a certain degree, increasing the reaction pH to 11.8, controlling the reaction temperature to be 65.0 ℃ and the ammonia concentration to be 5.0 g/L;
step 10, continuing feeding according to the step 9, determining the number of crystal nuclei of smaller particles according to the height ratio of the bimodal peak in the required product, reducing the reaction pH to 11.35 when the crystal nuclei of the smaller particles in the reaction kettle reach the target requirement, controlling the reaction temperature to be 65.0 ℃ and the ammonia concentration to be 5.0 g/L;
step 11, continuing feeding according to the step 10, stopping feeding when the particle size of the materials in the reaction kettle is detected to meet the required requirement, namely the particle distribution is consistent with the target requirement, and continuing stirring and aging for 1-2 hours;
step 12, adding the aged slurry obtained in the step 11 into filter-pressing washing equipment for washing and filter pressing, firstly washing the slurry for 0.5 to 2 hours by using a sodium hydroxide solution with the concentration of 2mol/L, and washing the slurry by using pure water after filtering;
and step 13, carrying out filter pressing and dehydration on the washed material obtained in the step 12, and then sending the material to a drying process, and after drying is finished, sequentially carrying out sieving and demagnetizing to obtain the nickel-cobalt-manganese hydroxide with the particle size in the target in bimodal distribution.
Example 2
Has a chemical formula of Ni0.5Co0.2Mn0.3(OH)2The nickel-cobalt-manganese hydroxide with bimodal distribution of particle sizes is determined to be spheroidal in microscopic morphology by an analytical scanning electron microscope methodParticles; the particle size distribution diagram is determined to be bimodal by a particle size analysis laser diffraction method, the bimodal peak positions are respectively positioned at 5.0 mu m and 10.8 mu m, the height ratio of the particle size distribution peak value of the smaller particles to the particle size distribution peak value of the larger particles is 0.63, the sphericity index phi of the particles is 1.0-1.6, and the tap density is determined to be more than or equal to 2.3g/cm by a tap density instrument3. The preparation method comprises the following steps:
step 1, according to the molar ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide with the required particle size in bimodal distribution, namely 5: 2: 3, selecting soluble salts of nickel, cobalt and manganese as raw materials;
step 2, preparing the nickel, cobalt and manganese soluble salts selected in the step 1 and pure water into a mixed salt solution with the total metal ion concentration of 2.05 mol/L;
step 3, preparing a sodium hydroxide solution with the concentration of 10.5 mol/L;
step 4, preparing ammonia water with the mass concentration of 9.5% as a complexing agent;
step 5, opening a jacket of the reaction kettle for water inlet and water return, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 6, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a base solution for starting up the reaction, wherein the pH value of the base solution is 11.8, and the ammonia concentration is 5.0 g/L;
step 7, adding the mixed metal salt solution prepared in the step 2, the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 into a reaction kettle in a concurrent flow manner for reaction, and controlling the reaction temperature to be 65.0 ℃, the pH to be 11.8 and the ammonia concentration to be 5.0 g/L;
step 8, continuing feeding according to the step 7, determining the number of crystal nuclei of larger particles according to the height ratio of the bimodal peak in the required product, reducing the reaction pH to 11.35 when the crystal nuclei of the larger particles in the reaction kettle reach the target requirement, controlling the reaction temperature to be 65.0 ℃ and the ammonia concentration to be 5.0 g/L; meanwhile, after the liquid level in the reaction kettle reaches the discharging requirement, starting a thickener to discharge, and maintaining the liquid level in the reaction kettle to be stable;
step 9, continuing feeding according to the step 8, when the particle size of the particles in the reaction kettle is 7.5 mu m, indicating that the crystal nucleus of larger particles grows to a certain degree, increasing the reaction pH to 11.8, controlling the reaction temperature to be 65.0 ℃ and the ammonia concentration to be 5.0 g/L;
step 10, continuing feeding according to the step 9, determining the number of crystal nuclei of smaller particles according to the height ratio of the bimodal peak in the required product, reducing the reaction pH to 11.35 when the crystal nuclei of the smaller particles in the reaction kettle reach the target requirement, controlling the reaction temperature to be 65.0 ℃ and the ammonia concentration to be 5.0 g/L;
step 11, continuing feeding according to the step 10, stopping feeding when the particle size of the materials in the reaction kettle is detected to meet the required requirement, namely the particle distribution is consistent with the target requirement, and continuing stirring and aging for 1-2 hours;
step 12, adding the aged slurry obtained in the step 11 into filter-pressing washing equipment for washing and filter pressing, firstly washing the slurry for 0.5 to 2 hours by using a sodium hydroxide solution with the concentration of 2mol/L, and washing the slurry by using pure water after filtering;
and step 13, carrying out filter pressing and dehydration on the washed material obtained in the step 12, and then sending the material to a drying process, and after drying is finished, sequentially carrying out sieving and demagnetizing to obtain the nickel-cobalt-manganese hydroxide with the particle size in the target in bimodal distribution.
Example 3
Has a chemical formula of Ni0.5Co0.2Mn0.3(OH)2The nickel-cobalt-manganese hydroxide with bimodal distribution of particle sizes is determined to be spheroidal particles in microscopic morphology by an analytical scanning electron microscope method; the particle size distribution diagram is determined to be bimodal by a particle size analysis laser diffraction method, the bimodal peak positions are respectively located at 3.5 mu m and 7.5 mu m, the height ratio of the particle size distribution peak value of the smaller particles to the particle size distribution peak value of the larger particles is 1.5, the sphericity index phi of the particles is 1.0-1.6, and the tap density is determined to be more than or equal to 2.3g/cm by a tap density instrument3. The preparation method comprises the following steps:
step 1, according to the molar ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide with the required particle size in bimodal distribution, namely 5: 2: 3, selecting soluble salts of nickel, cobalt and manganese as raw materials;
step 2, preparing the nickel, cobalt and manganese soluble salts selected in the step 1 and pure water into a mixed salt solution with the total metal ion concentration of 1.5 mol/L;
step 3, preparing a sodium hydroxide solution with the concentration of 4.0 mol/L;
step 4, preparing ammonia water with the mass concentration of 21% as a complexing agent;
step 5, opening a jacket of the reaction kettle for water inlet and water return, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 6, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a base solution for starting up the reaction, wherein the pH value of the base solution is 11.9, and the ammonia concentration is 6.0 g/L;
step 7, adding the mixed metal salt solution prepared in the step 2, the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 into a reaction kettle in a concurrent flow manner for reaction, and controlling the reaction temperature to be 50.0 ℃, the pH to be 11.9 and the ammonia concentration to be 6.0 g/L;
step 8, continuing feeding according to the step 7, determining the number of crystal nuclei of larger particles according to the height ratio of the bimodal peak in the required product, reducing the reaction pH to 10.9 when the crystal nuclei of the larger particles in the reaction kettle reach the target requirement, controlling the reaction temperature to be 50.0 ℃ and the ammonia concentration to be 6.0 g/L; meanwhile, after the liquid level in the reaction kettle reaches the discharging requirement, starting a thickener to discharge, and maintaining the liquid level in the reaction kettle to be stable;
step 9, continuing feeding according to the step 8, when the particle size of the particles in the reaction kettle is 5 microns, indicating that the crystal nucleus of larger particles grows to a certain degree, increasing the reaction pH to 11.9, controlling the reaction temperature to be 50.0 ℃ and the ammonia concentration to be 6.0 g/L;
step 10, continuing feeding according to the step 9, determining the number of crystal nuclei of smaller particles according to the height ratio of the bimodal peak in the required product, reducing the reaction pH to 10.9 when the crystal nuclei of the smaller particles in the reaction kettle reach the target requirement, controlling the reaction temperature to be 50.0 ℃ and the ammonia concentration to be 6.0 g/L;
step 11, continuing feeding according to the step 10, stopping feeding when the particle size of the materials in the reaction kettle is detected to meet the required requirement, namely the particle distribution is consistent with the target requirement, and continuing stirring and aging for 1-2 hours;
step 12, adding the aged slurry obtained in the step 11 into filter-pressing washing equipment for washing and filter pressing, firstly washing the slurry for 0.5 to 2 hours by using a sodium hydroxide solution with the concentration of 1mol/L, and washing the slurry by using pure water after filtering;
and step 13, carrying out filter pressing and dehydration on the washed material obtained in the step 12, and then sending the material to a drying process, and after drying is finished, sequentially carrying out sieving and demagnetizing to obtain the nickel-cobalt-manganese hydroxide with the particle size in the target in bimodal distribution.
The invention provides a preparation method of nickel-cobalt-manganese hydroxide with particle size in bimodal distribution, which has the following reaction principle:
if preparing the nickel-cobalt-manganese hydroxide with the particle size of bimodal distribution, the bimodal peak positions of which are respectively positioned at a mu m and b mu m (a is more than or equal to 3 and less than or equal to 6 and b is more than or equal to 8 and less than or equal to 15) and the ratio of the peak value of the particle size distribution of the smaller particles to the peak value of the particle size distribution of the larger particles is 0.5: preparing raw and auxiliary materials, preparing a base solution, starting feeding, wherein at the moment, under a higher pH value, a reaction system generates crystal nuclei for preparing larger particles, the longer the feeding time is, the more the crystal nuclei are generated, and when the number of the crystal nuclei reaches the required larger particle number, if the target number is m; reducing the pH value, starting the crystal nucleus to grow, when the crystal nucleus grows to c mu m (c is less than or equal to b), indicating that the crystal nucleus of larger particles grows to a certain degree, improving the reaction pH value, starting the reaction system to generate the crystal nucleus for preparing smaller particles, when the number of the crystal nuclei reaches the required number of smaller particles, namely 0.5m, reducing the pH value again, starting the crystal nucleus of smaller particles to grow, meanwhile, continuing to grow the crystal nucleus of larger particles which grows to a certain degree, and when the crystal nucleus of a large number of larger particles grows to b mu m, also growing to a mu m by the crystal nucleus of smaller particles, thereby obtaining the nickel-cobalt-manganese hydroxide which meets the target peak position and peak value.
In the whole reaction process, the smaller particles are generated when the larger particles exist, namely the small particle size is generated under the condition of higher solid content, and when the solid particles exist, the dispersity of small particle crystal nuclei is increased, the small particles are prevented from being agglomerated to form aggregates, so that the spherical shape is improvedDegree and density; meanwhile, under the action of ceaseless impact of small particles, the sphericity and the density of large particles tend to be better; the small particles are further doped in gaps of the large particles, so that the integral tap density is further improved, and the tap density of the product is more than or equal to 2.3g/cm3。

Claims (10)

1. The nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution is characterized in that the nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution is measured to be spherical-like particles in a microscopic morphology by an analytical scanning electron microscope method; the particle size distribution graph is determined to be bimodal through a particle size analysis laser diffraction method, the bimodal peak positions are respectively located within 3-6 microns and 8-15 microns, and the height ratio of the bimodal peak values is 0.25-4.
2. The nickel-cobalt-manganese hydroxide with the bimodal particle size distribution as claimed in claim 1, wherein the sphericity index Φ = Di/Dc, Di is the maximum inscribed sphere radius of the particles, and Dc is the minimum inscribed sphere radius of the same particles, is 1.0-1.6.
3. The nickel cobalt manganese hydroxide with a bimodal particle size distribution as claimed in claim 1, wherein the nickel cobalt manganese hydroxide with a bimodal particle size distribution is formed from NixCoyMnz(OH)2Wherein 0.30. ltoreq. x.ltoreq.0.92, 0. ltoreq. y.ltoreq.0.50, 0. ltoreq. z.ltoreq.0.50, and x + y + z = 1.
4. The nickel-cobalt-manganese hydroxide with bimodal particle size distribution according to claim 1, wherein the tap density is 2.3g/cm or more as measured by a tap densitometer3。
5. The preparation method of the nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution is characterized by comprising the following steps of:
step 1, according to the molar ratio of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide with the required particle size in bimodal distribution, namely x: y: z, selecting soluble salts of nickel, cobalt and manganese as raw materials;
step 2, preparing the nickel, cobalt and manganese soluble salts selected in the step 1 and pure water into a mixed salt solution with the total metal ion concentration of 1.2-2.7 mol/L;
step 3, preparing a sodium hydroxide solution with the concentration of 3.0-12.0 mol/L;
step 4, preparing ammonia water with the mass concentration of 5-30% as a complexing agent;
step 5, opening a jacket of the reaction kettle for water inlet and water return, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 6, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a bottom solution for starting up the reaction;
step 7, adding the mixed metal salt solution prepared in the step 2, the sodium hydroxide solution prepared in the step 3 and the ammonia water prepared in the step 4 into a reaction kettle in a concurrent flow manner for reaction, and controlling the reaction temperature, the pH value and the ammonia concentration;
step 8, continuing feeding according to the step 7, reducing the reaction pH when the crystal nucleus amount in the reaction kettle reaches the target requirement, and continuing to control the reaction temperature, the ammonia concentration and the like; meanwhile, after the liquid level in the reaction kettle reaches the discharging requirement, starting a thickener to discharge, and maintaining the liquid level in the reaction kettle to be stable;
step 9, continuing feeding according to the step 8, increasing the reaction pH when the particle size of the particles in the reaction kettle is 5-12 mu m, and continuing to control the reaction temperature, the ammonia concentration and the like;
step 10, continuing feeding according to the step 9, reducing the reaction pH when the crystal nucleus amount in the reaction kettle reaches the target requirement, and continuing to control the reaction temperature, the ammonia concentration and the like;
step 11, continuing feeding according to the step 10, stopping feeding when the particle size of the materials in the reaction kettle is detected to meet the required requirement, and continuing stirring and aging for 1-2 hours;
step 12, adding the aged slurry obtained in the step 11 into filter-pressing washing equipment for washing and filter pressing, firstly washing the slurry for 0.5 to 2 hours by using a sodium hydroxide solution with the concentration of 0.1 to 5mol/L, and washing the slurry by using pure water after filtering;
and step 13, carrying out filter pressing and dehydration on the washed material obtained in the step 12, then sending the material to a drying process, and after drying is finished, sequentially carrying out sieving and demagnetizing to obtain the nickel-cobalt-manganese hydroxide with the particle size in bimodal distribution.
6. The method for preparing nickel-cobalt-manganese hydroxide with bimodal particle size distribution according to claim 5, wherein: in the step 6, the pH value of the starting-up base solution is 11.2-12.4, and the ammonia concentration is 1.0-14.0 g/L.
7. The method for preparing nickel-cobalt-manganese hydroxide with bimodal particle size distribution according to claim 5, wherein: in the step 7, the reaction temperature is controlled to be 50.0-70.0 ℃, the pH is controlled to be 11.2-12.4, and the ammonia concentration is controlled to be 1.0-14.0 g/L.
8. The method for preparing nickel-cobalt-manganese hydroxide with bimodal particle size distribution according to claim 5, wherein: in the step 8, the reaction pH is reduced to 10.5-11.2, the reaction temperature is controlled to be 50.0-70.0 ℃, and the ammonia concentration is 1.0-14.0 g/L.
9. The method for preparing nickel-cobalt-manganese hydroxide with bimodal particle size distribution according to claim 5, wherein: in the step 9, the reaction pH is increased to 11.2-12.4, the reaction temperature is controlled to be 50.0-70.0 ℃, and the ammonia concentration is 1.0-14.0 g/L.
10. The method for preparing nickel-cobalt-manganese hydroxide with bimodal particle size distribution according to claim 5, wherein: in the step 10, the reaction pH is reduced to 10.5-11.2, the reaction temperature is controlled to be 50.0-70.0 ℃, and the ammonia concentration is 1.0-14.0 g/L.
CN202010109292.8A 2020-02-22 2020-02-22 Nickel-cobalt-manganese hydroxide with particle size in bimodal distribution and preparation method thereof Pending CN111204821A (en)

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