CN108314094B - Preparation method of small-particle nickel cobalt aluminum hydroxide - Google Patents

Preparation method of small-particle nickel cobalt aluminum hydroxide Download PDF

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CN108314094B
CN108314094B CN201810084041.1A CN201810084041A CN108314094B CN 108314094 B CN108314094 B CN 108314094B CN 201810084041 A CN201810084041 A CN 201810084041A CN 108314094 B CN108314094 B CN 108314094B
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蒋央芳
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Abstract

The invention discloses a preparation method of small-particle nickel cobalt aluminum hydroxide. Preparing a nickel-cobalt-aluminum mixed solution, an ammonium bicarbonate solution and an ammonium monohydrogen phosphate solution; adding the mixed solution, the ammonium bicarbonate solution and the ammonium monohydrogen phosphate solution into the base solution in a parallel flow manner, and after the addition is finished, dropwise adding hydrogen peroxide and the ammonium bicarbonate solution for continuous reaction; filtering and slurrying, then adding ammonia water into the slurried material, heating for reaction, and adding hot pure water for washing; and (3) drying by adopting a disc dryer, and then screening, deironing and mixing to obtain small-particle nickel cobalt aluminum hydroxide. The method can obtain the nickel-cobalt-aluminum hydroxide with the particle size of less than 2.5 microns, has high sphericity and tap density, realizes phosphorus doping, and has simple process and low energy consumption.

Description

Preparation method of small-particle nickel cobalt aluminum hydroxide
Technical Field
The invention relates to a preparation method of small-particle nickel cobalt aluminum hydroxide, belonging to the field of new energy materials of lithium batteries.
Background
The performance of the power battery is a limiting factor determining the development of the electric automobile, the popularization and development of the electric automobile are restricted due to the problems of insufficient cruising ability, low charging speed, high cost and the like of the power battery at the present stage, the main reason that many consumers are forbidden is also the main reason, and the market popularization degree of the electric automobile is influenced to a great extent by the cost performance of the power lithium battery. The positive electrode material is a key material of the power lithium battery, the energy density of the positive electrode material is closely related to the endurance mileage of the electric automobile, and the cost of the positive electrode material is about 1/3 of the cost of the lithium battery cell, so that the development of the positive electrode material with high energy density, long service life, high safety and low cost is important for large-scale commercial use of the power lithium battery and the electric automobile.
At present, the technical routes of the power lithium battery anode materials at home and abroad mainly have 3 genres: lithium iron phosphate pie, lithium manganate pie, ternary pie [ lithium Nickel Cobalt Aluminate (NCA) and lithium Nickel Cobalt Manganese (NCM) ]. The battery using lithium iron phosphate as the anode material has long charge-discharge cycle life, but has the defects of large differences in energy density, high-low temperature performance and charge-discharge rate characteristics, high production cost and development bottleneck of the lithium iron phosphate battery technology and application; the lithium manganate battery has low energy density and poor cycling stability and storage performance at high temperature, so the lithium manganate is only used as a positive electrode material of the international 1 st generation power lithium battery; the multi-element material is increasingly concerned and accepted by the industry due to the double advantages of comprehensive performance and cost, and gradually surpasses the technical route that lithium iron phosphate and lithium manganate become mainstream. In particular, represented by a Tesla (Tesla) electric vehicle outstanding in the different military of 2013, the service life of TeslaModel S pushed by the TeslaModel S can reach 480km, and the anode material adopted by a cylindrical battery cell is NCA. From the view point of the energy density of the battery and the endurance mileage of the electric vehicle, the ternary system containing nickel (Ni) has obvious advantages, in particular to the battery made of the high Ni ternary system (NCA) material.
The demand of high energy density power lithium battery drives the application and continuous promotion of high Ni unitary material with high specific capacity, and with the hot sale of American Tesla, lithium battery enterprises such as Panasonic, AESC, Nissan in Japan, and LGC, SKI and Samsung in Korea all put the material selection emphasis on high nickel multi-component materials, and conventional LiNi is used1/3Co1/3Mn1/3O2(NCM 111 for short) and gradually turning to a multi-component material LiNi with high nickel content0.5Co0.2Mn0.3O2(NCM 523) and LiNi0.6Co0.2Mn0.2O2(abbreviated as NCM622) and LiNi0.8Co0.1Mn0.1O2(NCM 811 for short) and an NCA material having a Ni content of 80 to 89% higher than that of nickel.
For the nickel cobalt lithium aluminate anode material, in order to improve the compaction density, that is, the energy density, the existing method is to mix and dope the nickel cobalt lithium aluminate with large particle size and the nickel cobalt lithium aluminate with small particle size, so as to improve the compaction density, generally the D50 of the nickel cobalt lithium aluminate with small particle size is required to be less than 3 microns, and then the particle size of the nickel cobalt aluminum hydroxide is required to be less than 2.5 microns, but the nickel cobalt aluminum hydroxide with particle size less than 2.5 microns can not be obtained by the conventional coprecipitation process, and the obtained nickel cobalt aluminum hydroxide with small particle size has poor sphericity, small tap density and high energy consumption.
Disclosure of Invention
In view of the above, the invention provides a method for preparing small-particle nickel cobalt aluminum hydroxide, which can obtain nickel cobalt aluminum hydroxide with a particle size of less than 2.5 micrometers, has high sphericity and tap density, realizes phosphorus doping, and has the advantages of simple process and low energy consumption.
The invention solves the technical problems by the following technical means:
a preparation method of small-particle nickel cobalt aluminum hydroxide comprises the following steps:
(1) preparing a solution, mixing and dissolving nickel, cobalt and aluminum salts into pure water to obtain a nickel, cobalt and aluminum mixed solution, adding an acid-alkali solution to adjust the pH of the mixed solution to 1.0-1.2, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then putting the mixed solution into a constant temperature tank to keep the temperature at 30-35 ℃; adding pure water into ammonium bicarbonate for dissolving, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then placing the solution into a constant temperature tank to be constant in temperature to be 30-35 ℃; adding ammonium monohydrogen phosphate into pure water for dissolving, then removing iron through a fluid iron remover, performing precision filtration through a precision filter, and then putting the mixture into a constant temperature tank to keep the temperature at 30-35 ℃;
(2) reacting, namely adding the mixed solution obtained in the step (1), an ammonium bicarbonate solution and an ammonium monohydrogen phosphate solution into a base solution in a parallel flow manner, stabilizing the flow rates of the mixed solution and the ammonium monohydrogen phosphate solution, adjusting the flow rate of the ammonium bicarbonate solution to maintain the pH value of 6-6.5 in the reaction process, keeping the time of adding the materials for 60-90min, keeping the temperature of 35-40 ℃ in the feeding process, simultaneously stirring at the speed of 250-350r/min, simultaneously heating to 50-60 ℃ after adding the materials, maintaining the temperature, dropwise adding hydrogen peroxide and the ammonium bicarbonate solution to maintain the pH value of 6-6.5, continuing to react for 10-30min after adding the materials, then carrying out solid-liquid separation to obtain a first filter residue and a first filtrate, adding hot pure water into the first filter residue for washing, and washing until the conductivity of washing water is less than or equal to 100 mu S/cm;
(3) precipitating and converting, namely adding the first filter residue washed in the step (2) into a polyolefin hyperdispersant solution for slurrying, wherein the mass ratio of the first filter residue to the polyolefin hyperdispersant solution is 1:5-10, heating to 40-50 ℃ after slurrying, keeping the temperature constant, then adding ammonia water into the slurried material, maintaining the pH value of the dropwise adding process to be 7.5-8.0, heating to 75-85 ℃ after adding, stirring for reacting for 30-40min, performing solid-liquid separation to obtain a second filter residue and a second filtrate, and adding the second filter residue into hot pure water washing water to ensure that the conductivity is not more than 20 mu S/cm;
(4) and (4) drying the second filter residue washed in the step (3) by using a disc type dryer, and then screening, removing iron and mixing to obtain small-particle nickel cobalt aluminum hydroxide.
The purity of the nickel cobalt aluminum salt in the step (1) is battery grade, the total mole number of the finally obtained nickel cobalt aluminum mixed solution is 1.5-2mol/L, the concentration of ammonium bicarbonate is 0.5-0.6mol/L, the concentration of ammonium monohydrogen phosphate is 1-1.2mol/L, a ceramic filter element is adopted by the precision filter, and the aperture of the ceramic filter element is 20-100 nm.
The concentration of ammonium monohydrogen phosphate in the base solution in the step (2) is 0.1-0.12mol/L, meanwhile, the ammonium bicarbonate solution is added to ensure that the pH of the base solution is 6-6.5, the volume of the base solution is 1/15-1/12 of the total volume of the added mixed solution, the ammonium bicarbonate solution and the ammonium monohydrogen phosphate solution, the mixed solution and the ammonium monohydrogen phosphate solution are uniformly added into the base solution, the molar ratio of nickel cobalt aluminum in the mixed solution to the total molar number of ammonium monohydrogen phosphate in the ammonium monohydrogen phosphate solution is maintained to be 3:2.1-2.15, the mass fraction of the added hydrogen peroxide is 25-30%, and the molar number of the added hydrogen peroxide is 2-2.5 times of the total molar number of nickel cobalt ions in the mother solution after the feeding is finished.
And (3) in the step (2), the temperature of hot pure water used for washing the first filter residue is 70-75 ℃, the first filtrate is mixed with washing water for washing the first filter residue, an acid solution is added to adjust the pH of the solution to be 2-3, TBP is added to perform extraction, phosphoric acid is extracted, ammonia water is added to perform washing and recovery to obtain ammonium phosphate, and raffinate is concentrated, evaporated and crystallized to obtain ammonium salt.
In the step (3), the concentration of the polyolefin hyperdispersant solution is 0.01-0.02%, the stirring speed during slurrying is 300-.
And (3) mixing the second filtrate with washing water for washing the second filter residue, adding ammonia water to adjust the pH to 7.5-8, performing precise filtration, concentrating and crystallizing to obtain ammonium monohydrogen phosphate, and returning the solution to obtain an ammonium monohydrogen phosphate solution.
And (4) drying until the moisture content is lower than 0.5%, screening by adopting a 225-mesh sieve, removing iron by adopting an electromagnetic iron remover, wherein the magnetic induction intensity of the electromagnetic iron remover is 15000-25000 gauss.
The method comprises the steps of firstly preparing a nickel-cobalt-aluminum phosphate precipitate, then adding ammonia water, converting the phosphate precipitate into a hydroxide precipitate to obtain nickel-cobalt-aluminum hydroxide, and when preparing the nickel-cobalt-aluminum precipitate, controlling reaction conditions to obtain the nickel-cobalt-aluminum phosphate precipitate with small particle size and uniform nickel-cobalt-aluminum distribution, wherein the indexes of the obtained phosphate precipitate are as follows:
Figure GDA0002196907240000031
then adding ammonia water for precipitation conversion, converting into hydroxide precipitate, and then processing to finally obtain the small-particle nickel-cobalt-aluminum hydroxide with the following indexes:
index (I) Ni+Co+Al P D10 D50 D90
Numerical value 60-61.5％ 2000-2500ppm 0.4-0.6μm 1.2-1.5μm 2.0-2.3μm
D100 Cd Mg Na Mn Ca
＜5μm ＜10ppm ＜10ppm ＜10ppm ＜10ppm ＜10ppm
K Zn Cu Ti Pb Si
＜10ppm ＜10ppm ＜10ppm ＜10ppm ＜10ppm ＜10ppm
Tap density Sulfate radical Chloride ion BET pH Morphology of
1.4-1.6g/mL ＜20ppm ＜20ppm 5-8m2/g 6-8 Spherical shape
The nickel hydroxide, cobalt and aluminum hydroxide obtained by the process is green powder, has good fluidity and is spherical in shape.
In order to improve the recovery rate of cobalt and nickel, hydrogen peroxide is added for oxidation when phosphate precipitation is adopted, so that non-precipitated nickel and cobalt ions can be further precipitated, and the recovery rate of nickel and cobalt is improved.
Finally, the mother liquor after the conversion is precipitated and concentrated and crystallized to obtain ammonium monohydrogen phosphate for returning use, thereby further reducing the cost.
The invention has the beneficial effects that: can obtain nickel cobalt aluminum hydroxide with the grain diameter less than 2.5 microns, has high sphericity and tap density, realizes the doping of phosphorus, and has simple process and low energy consumption.
Detailed Description
The present invention will be described in detail with reference to the following specific examples, in which the preparation method of small-particle nickel cobalt aluminum hydroxide of the present embodiment comprises the following steps:
(1) preparing a solution, mixing and dissolving nickel, cobalt and aluminum salts into pure water to obtain a nickel, cobalt and aluminum mixed solution, adding an acid-alkali solution to adjust the pH of the mixed solution to 1.0-1.2, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then putting the mixed solution into a constant temperature tank to keep the temperature at 30-35 ℃; adding pure water into ammonium bicarbonate for dissolving, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then placing the solution into a constant temperature tank to be constant in temperature to be 30-35 ℃; adding ammonium monohydrogen phosphate into pure water for dissolving, then removing iron through a fluid iron remover, performing precision filtration through a precision filter, and then putting the mixture into a constant temperature tank to keep the temperature at 30-35 ℃;
(2) reacting, namely adding the mixed solution obtained in the step (1), an ammonium bicarbonate solution and an ammonium monohydrogen phosphate solution into a base solution in a parallel flow manner, stabilizing the flow rates of the mixed solution and the ammonium monohydrogen phosphate solution, adjusting the flow rate of the ammonium bicarbonate solution to maintain the pH value of 6-6.5 in the reaction process, keeping the time of adding the materials for 60-90min, keeping the temperature of 35-40 ℃ in the feeding process, simultaneously stirring at the speed of 250-350r/min, simultaneously heating to 50-60 ℃ after adding the materials, maintaining the temperature, dropwise adding hydrogen peroxide and the ammonium bicarbonate solution to maintain the pH value of 6-6.5, continuing to react for 10-30min after adding the materials, then carrying out solid-liquid separation to obtain a first filter residue and a first filtrate, adding hot pure water into the first filter residue for washing, and washing until the conductivity of washing water is less than or equal to 100 mu S/cm;
(3) precipitating and converting, namely adding the first filter residue washed in the step (2) into a polyolefin hyperdispersant solution for slurrying, wherein the mass ratio of the first filter residue to the polyolefin hyperdispersant solution is 1:5-10, heating to 40-50 ℃ after slurrying, keeping the temperature constant, then adding ammonia water into the slurried material, maintaining the pH value of the dropwise adding process to be 7.5-8.0, heating to 75-85 ℃ after adding, stirring for reacting for 30-40min, performing solid-liquid separation to obtain a second filter residue and a second filtrate, and adding the second filter residue into hot pure water washing water to ensure that the conductivity is not more than 20 mu S/cm;
(4) and (4) drying the second filter residue washed in the step (3) by using a disc type dryer, and then screening, removing iron and mixing to obtain small-particle nickel cobalt aluminum hydroxide.
The purity of the nickel cobalt aluminum salt in the step (1) is battery grade, the total mole number of the finally obtained nickel cobalt aluminum mixed solution is 1.5-2mol/L, the concentration of ammonium bicarbonate is 0.5-0.6mol/L, the concentration of ammonium monohydrogen phosphate is 1-1.2mol/L, a ceramic filter element is adopted by the precision filter, and the aperture of the ceramic filter element is 20-100 nm.
The concentration of ammonium monohydrogen phosphate in the base solution in the step (2) is 0.1-0.12mol/L, meanwhile, the ammonium bicarbonate solution is added to ensure that the pH of the base solution is 6-6.5, the volume of the base solution is 1/15-1/12 of the total volume of the added mixed solution, the ammonium bicarbonate solution and the ammonium monohydrogen phosphate solution, the mixed solution and the ammonium monohydrogen phosphate solution are uniformly added into the base solution, the molar ratio of nickel cobalt aluminum in the mixed solution to the total molar number of ammonium monohydrogen phosphate in the ammonium monohydrogen phosphate solution is maintained to be 3:2.1-2.15, the mass fraction of the added hydrogen peroxide is 25-30%, and the molar number of the added hydrogen peroxide is 2-2.5 times of the total molar number of nickel cobalt ions in the mother solution after the feeding is finished.
And (3) in the step (2), the temperature of hot pure water used for washing the first filter residue is 70-75 ℃, the first filtrate is mixed with washing water for washing the first filter residue, an acid solution is added to adjust the pH of the solution to be 2-3, TBP is added to perform extraction, phosphoric acid is extracted, ammonia water is added to perform washing and recovery to obtain ammonium phosphate, and raffinate is concentrated, evaporated and crystallized to obtain ammonium salt.
In the step (3), the concentration of the polyolefin hyperdispersant solution is 0.01-0.02%, the stirring speed during slurrying is 300-.
And (3) mixing the second filtrate with washing water for washing the second filter residue, adding ammonia water to adjust the pH to 7.5-8, performing precise filtration, concentrating and crystallizing to obtain ammonium monohydrogen phosphate, and returning the solution to obtain an ammonium monohydrogen phosphate solution.
And (4) drying until the moisture content is lower than 0.5%, screening by adopting a 225-mesh sieve, removing iron by adopting an electromagnetic iron remover, wherein the magnetic induction intensity of the electromagnetic iron remover is 15000-25000 gauss.
The indexes of the finally obtained small-particle nickel hydroxide, cobalt and aluminum hydroxide are as follows:
index (I) Ni+Co+Al P D10 D50 D90
Numerical value 60-61.5％ 2000-2500ppm 0.4-0.6μm 1.2-1.5μm 2.0-2.3μm
D100 Cd Mg Na Mn Ca
＜5μm ＜10ppm ＜10ppm ＜10ppm ＜10ppm ＜10ppm
K Zn Cu Ti Pb Si
＜10ppm ＜10ppm ＜10ppm ＜10ppm ＜10ppm ＜10ppm
Tap density Sulfate radical Chloride ion BET pH Morphology of
1.4-1.6g/mL ＜20ppm ＜20ppm 5-8m2/g 6-8 Spherical shape
Example 1
A preparation method of small-particle nickel cobalt aluminum hydroxide comprises the following steps:
(1) preparing a solution, mixing and dissolving nickel, cobalt and aluminum salt into pure water to obtain a nickel, cobalt and aluminum mixed solution, adding an acid-alkali solution to adjust the pH of the mixed solution to 1.15, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then putting the mixed solution into a constant temperature tank to keep the temperature at 31.5 ℃; adding pure water into ammonium bicarbonate for dissolving, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then placing the mixture into a constant temperature tank to keep the temperature at 31.5 ℃; adding ammonium monohydrogen phosphate into pure water for dissolving, then removing iron through a fluid iron remover, performing precision filtration through a precision filter, and then putting the mixture into a constant temperature tank to keep the temperature at 31.5 ℃;
(2) reacting, namely adding the mixed solution obtained in the step (1), an ammonium bicarbonate solution and an ammonium monohydrogen phosphate solution into a base solution in a concurrent flow manner, stabilizing the flow rates of the mixed solution and the ammonium monohydrogen phosphate solution, adjusting the flow rate of the ammonium bicarbonate solution to maintain the pH value of 6.35 in the reaction process, keeping the time of adding the materials for 80min, keeping the temperature of 36 ℃ in the feeding process, simultaneously stirring at 315r/min, simultaneously heating to 53 ℃ after adding the materials, keeping the temperature, dropwise adding a hydrogen peroxide solution and an ammonium bicarbonate solution, keeping the pH value at 6.35, continuing to react for 20min after adding, then carrying out solid-liquid separation to obtain a first filter residue and a first filtrate, adding hot pure water into the first filter residue for washing, and washing until the conductivity of washing water is less than or equal to 100 muS/cm;
(3) precipitating and converting, namely adding the first filter residue washed in the step (2) into a polyolefin hyperdispersant solution for slurrying, wherein the mass ratio of the first filter residue to the polyolefin hyperdispersant solution is 1:8, heating to 45 ℃ after slurrying, keeping the temperature constant, then adding ammonia water into the slurried material, maintaining the pH value in the dropwise adding process to be 7.8, heating to 79 ℃ after adding, stirring for reacting for 35min, carrying out solid-liquid separation to obtain a second filter residue and a second filtrate, and adding the second filter residue into hot pure water washing water, wherein the conductivity of the hot pure water washing water is not more than 20 mu S/cm;
(4) and (4) drying the second filter residue washed in the step (3) by using a disc type dryer, and then screening, removing iron and mixing to obtain small-particle nickel cobalt aluminum hydroxide.
The purity of the nickel cobalt aluminum salt in the step (1) is battery grade, the total mole number of the finally obtained nickel cobalt aluminum mixed solution is 1.8mol/L, the concentration of ammonium bicarbonate is 0.54mol/L, the concentration of ammonium monohydrogen phosphate is 1.12mol/L, the precision filter adopts a ceramic filter element, and the aperture of the ceramic filter element is 80 nm.
The concentration of ammonium monohydrogen phosphate in the base solution in the step (2) is 0.11mol/L, meanwhile, an ammonium bicarbonate solution is added to enable the pH of the base solution to be 6.35, the volume of the base solution is 1/14 of the total volume of the added mixed solution, the ammonium bicarbonate solution and the ammonium monohydrogen phosphate solution, the mixed solution and the ammonium monohydrogen phosphate solution are added into the base solution at an even speed, the molar ratio of the total mole number of nickel and cobalt and aluminum of the mixed solution to the mole number of ammonium monohydrogen phosphate in the ammonium monohydrogen phosphate solution is maintained to be 3:2.12, the mass fraction of the added hydrogen peroxide is 28%, and the mole number of the added hydrogen peroxide is 2.15 times of the total mole number of nickel and cobalt ions in the mother solution after the addition is finished.
And (3) in the step (2), the temperature of hot pure water used for washing the first filter residue is 72.5 ℃, the first filtrate is mixed with washing water for washing the first filter residue, an acid solution is added to adjust the pH of the solution to be 2.3, TBP is added to perform extraction, phosphoric acid is extracted, ammonia water is added to perform washing and recovery to obtain ammonium phosphate, and raffinate is concentrated, evaporated and crystallized to obtain ammonium salt.
In the step (3), the concentration of the polyolefin hyper-dispersant solution is 0.013%, the stirring speed during slurry making is 320r/min, the slurry making time is 35min, the concentration of ammonia water is 5.3mol/L, and the total time for finishing ammonia water dripping is 41 min.
And (3) mixing the second filtrate with washing water for washing the second filter residue, adding ammonia water to adjust the pH to 7.8, performing precise filtration, concentrating and crystallizing to obtain ammonium monohydrogen phosphate, and returning to the solution preparation to obtain an ammonium monohydrogen phosphate solution.
And (4) drying until the moisture content is lower than 0.5%, screening by adopting a 225-mesh sieve, removing iron by adopting an electromagnetic iron remover, and controlling the magnetic induction intensity of the electromagnetic iron remover to 20000 gausses.
The indexes of the finally obtained small-particle nickel hydroxide, cobalt and aluminum hydroxide are as follows:
index (I) Ni+Co+Al P D10 D50 D90
Numerical value 60.5％ 2230ppm 0.45μm 1.37μm 2.18μm
D100 Cd Mg Na Mn Ca
4.87μm 6ppm 7ppm 8ppm 5.1ppm 8.1ppm
K Zn Cu Ti Pb Si
1.2ppm 2.8ppm 0.25ppm 5.6ppm 2.8ppm 8.7ppm
Tap density Sulfate radical Chloride ion BET pH Morphology of
1.52g/mL 18.4ppm 5.9ppm 5.8m2/g 6.8 Spherical shape
Example 2
A preparation method of small-particle nickel cobalt aluminum hydroxide comprises the following steps:
(1) preparing a solution, mixing and dissolving nickel, cobalt and aluminum salt into pure water to obtain a nickel, cobalt and aluminum mixed solution, adding an acid-alkali solution to adjust the pH of the mixed solution to 1.08, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then putting the mixed solution into a constant temperature tank to keep the temperature at 33.8 ℃; adding pure water into ammonium bicarbonate for dissolving, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then placing the mixture into a constant temperature tank to keep the temperature at 33.8 ℃; adding ammonium monohydrogen phosphate into pure water for dissolving, then removing iron through a fluid iron remover, performing precision filtration through a precision filter, and then placing the mixture into a constant temperature tank to keep the temperature at 33.8 ℃;
(2) reacting, namely adding the mixed solution obtained in the step (1), an ammonium bicarbonate solution and an ammonium monohydrogen phosphate solution into a base solution in a concurrent flow manner, stabilizing the flow rates of the mixed solution and the ammonium monohydrogen phosphate solution, adjusting the flow rate of the ammonium bicarbonate solution to maintain the pH value of 6.15 in the reaction process, keeping the time of adding the materials for 70min, keeping the temperature of 38.5 ℃ in the feeding process, simultaneously stirring at 275r/min, simultaneously heating to 52 ℃ after adding the materials, keeping the temperature, dropwise adding a hydrogen peroxide solution and an ammonium bicarbonate solution to maintain the pH value of 6.15, continuing the reaction for 20min after adding, then carrying out solid-liquid separation to obtain a first filter residue and a first filtrate, adding hot pure water into the first filter residue for washing, and washing until the conductivity of washing water is less than or equal to 100 mu S/cm;
(3) precipitating and converting, namely adding the first filter residue washed in the step (2) into a polyolefin hyperdispersant solution for slurrying, wherein the mass ratio of the first filter residue to the polyolefin hyperdispersant solution is 1:9, heating to 43 ℃ after slurrying, keeping the temperature constant, then adding ammonia water into the slurried material, maintaining the pH value in the dropwise adding process to be 7.9, heating to 79 ℃ after adding, stirring for reaction for 33min, carrying out solid-liquid separation to obtain a second filter residue and a second filtrate, and adding the second filter residue into hot pure water washing water, wherein the conductivity of the hot pure water washing water is not more than 20 mu S/cm;
(4) and (4) drying the second filter residue washed in the step (3) by using a disc type dryer, and then screening, removing iron and mixing to obtain small-particle nickel cobalt aluminum hydroxide.
The purity of the nickel cobalt aluminum salt in the step (1) is battery grade, the total mole number of the finally obtained nickel cobalt aluminum mixed solution is 1.8mol/L, the concentration of ammonium bicarbonate is 0.55mol/L, the concentration of ammonium monohydrogen phosphate is 1.15mol/L, the precision filter adopts a ceramic filter element, and the aperture of the ceramic filter element is 40 nm.
The concentration of ammonium monohydrogen phosphate in the base solution in the step (2) is 0.112mol/L, meanwhile, an ammonium bicarbonate solution is added to enable the pH of the base solution to be 6.15, the volume of the base solution is 1/13 of the total volume of the added mixed solution, the ammonium bicarbonate solution and the ammonium monohydrogen phosphate solution, the mixed solution and the ammonium monohydrogen phosphate solution are added into the base solution at an even speed, the molar ratio of the total mole number of nickel and cobalt and aluminum of the mixed solution to the mole number of ammonium monohydrogen phosphate in the ammonium monohydrogen phosphate solution is maintained to be 3:2.12, the mass fraction of the added hydrogen peroxide is 27%, and the mole number of the added hydrogen peroxide is 2.35 times of the total mole number of nickel and cobalt ions in the mother solution after the addition is finished.
And (3) in the step (2), the temperature of hot pure water used for washing the first filter residue is 73.5 ℃, the first filtrate is mixed with washing water for washing the first filter residue, an acid solution is added to adjust the pH of the solution to be 2.15, TBP is added to perform extraction, phosphoric acid is extracted, ammonia water is added to perform washing and recovery to obtain ammonium phosphate, and raffinate is concentrated, evaporated and crystallized to obtain ammonium salt.
In the step (3), the concentration of the polyolefin hyper-dispersant solution is 0.013%, the stirring speed during slurry making is 315r/min, the slurry making time is 45min, the concentration of ammonia water is 5.5mol/L, and the total time for finishing ammonia water dripping is 41 min.
And (3) mixing the second filtrate with washing water for washing the second filter residue, adding ammonia water to adjust the pH to 7.85, performing precise filtration, concentrating and crystallizing to obtain ammonium monohydrogen phosphate, and returning to the solution preparation to obtain an ammonium monohydrogen phosphate solution.
And (4) drying until the moisture content is lower than 0.5%, screening by adopting a 225-mesh sieve, removing iron by adopting an electromagnetic iron remover, and controlling the magnetic induction intensity of the electromagnetic iron remover to 20000 gausses.
The indexes of the finally obtained small-particle nickel hydroxide, cobalt and aluminum hydroxide are as follows:
index (I) Ni+Co+Al P D10 D50 D90
Numerical value 60.8％ 2150ppm 0.47μm 1.39μm 2.17μm
D100 Cd Mg Na Mn Ca
4.68μm 3.2ppm 5.7ppm 2.9ppm 5.9ppm 6.8ppm
K Zn Cu Ti Pb Si
5.9ppm 7.1ppm 6.7ppm 3.8ppm 1.8ppm 4.9ppm
Tap density Sulfate radical Chloride ion BET pH Morphology of
1.51g/mL 13ppm 10.9ppm 6.8m2/g 7.2 Spherical shape
Example 3
A preparation method of small-particle nickel cobalt aluminum hydroxide comprises the following steps:
(1) preparing a solution, mixing and dissolving nickel, cobalt and aluminum salt into pure water to obtain a nickel, cobalt and aluminum mixed solution, adding an acid-alkali solution to adjust the pH of the mixed solution to 1.13, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then putting the mixed solution into a constant temperature tank to keep the temperature at 33.8 ℃; adding pure water into ammonium bicarbonate for dissolving, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then placing the mixture into a constant temperature tank to keep the temperature at 33.8 ℃; adding ammonium monohydrogen phosphate into pure water for dissolving, then removing iron through a fluid iron remover, performing precision filtration through a precision filter, and then placing the mixture into a constant temperature tank to keep the temperature at 33.8 ℃;
(2) reacting, namely adding the mixed solution obtained in the step (1), an ammonium bicarbonate solution and an ammonium monohydrogen phosphate solution into a base solution in a concurrent flow manner, stabilizing the flow rates of the mixed solution and the ammonium monohydrogen phosphate solution, adjusting the flow rate of the ammonium bicarbonate solution to maintain the pH value of the reaction process to be 6.25, keeping the time of adding the materials to be 80min, keeping the temperature of the feeding process to be 38 ℃, simultaneously stirring at the speed of 335r/min, simultaneously heating to 55 ℃ after the materials are added, keeping the temperature, dropwise adding a hydrogen peroxide solution and an ammonium bicarbonate solution, keeping the pH value to be 6.25, continuing to react for 25min after the materials are added, then carrying out solid-liquid separation to obtain a first filter residue and a first filtrate, adding hot pure water into the first filter residue for washing, and washing until the conductivity of washing water is less than or equal to 100 muS/;
(3) precipitating and converting, namely adding the first filter residue washed in the step (2) into a polyolefin hyperdispersant solution for slurrying, wherein the mass ratio of the first filter residue to the polyolefin hyperdispersant solution is 1:9, heating to 43 ℃ after slurrying, keeping the temperature constant, then adding ammonia water into the slurried material, maintaining the pH value in the dropwise adding process to be 7.9, heating to 79 ℃ after adding, stirring for reacting for 35min, carrying out solid-liquid separation to obtain a second filter residue and a second filtrate, and adding the second filter residue into hot pure water washing water, wherein the conductivity of the hot pure water washing water is not more than 20 mu S/cm;
(4) and (4) drying the second filter residue washed in the step (3) by using a disc type dryer, and then screening, removing iron and mixing to obtain small-particle nickel cobalt aluminum hydroxide.
The purity of the nickel cobalt aluminum salt in the step (1) is battery grade, the total mole number of the finally obtained nickel cobalt aluminum mixed solution is 1.85mol/L, the concentration of ammonium bicarbonate is 0.54mol/L, the concentration of ammonium monohydrogen phosphate is 1.12mol/L, the precision filter adopts a ceramic filter element, and the aperture of the ceramic filter element is 40 nm.
The concentration of ammonium monohydrogen phosphate in the base solution in the step (2) is 0.11mol/L, meanwhile, an ammonium bicarbonate solution is added to enable the pH of the base solution to be 6.25, the volume of the base solution is 1/12 of the total volume of the added mixed solution, the ammonium bicarbonate solution and the ammonium monohydrogen phosphate solution, the mixed solution and the ammonium monohydrogen phosphate solution are added into the base solution at an even speed, the molar ratio of the total mole number of nickel and cobalt and aluminum of the mixed solution to the mole number of ammonium monohydrogen phosphate in the ammonium monohydrogen phosphate solution is maintained to be 3:2.13, the mass fraction of the added hydrogen peroxide is 29%, and the mole number of the added hydrogen peroxide is 2.35 times of the total mole number of nickel and cobalt ions in the mother solution after the addition is finished.
And (3) in the step (2), the temperature of hot pure water used for washing the first filter residue is 72 ℃, the first filtrate is mixed with washing water for washing the first filter residue, then an acid solution is added to adjust the pH of the solution to be 2.5, then TBP is added to perform extraction, phosphoric acid is extracted, ammonia water is added to perform washing and recovery to obtain ammonium phosphate, and raffinate is subjected to concentration, evaporation and crystallization to obtain ammonium salt.
In the step (3), the concentration of the polyolefin hyper-dispersant solution is 0.015 percent, the stirring speed during slurrying is 325r/min, the slurrying time is 40min, the concentration of ammonia water is 5.3mol/L, and the total time of finishing dropping the ammonia water is 42 min.
And (3) mixing the second filtrate with washing water for washing the second filter residue, adding ammonia water to adjust the pH to 7.75, performing precise filtration, concentrating and crystallizing to obtain ammonium monohydrogen phosphate, and returning to the solution preparation to obtain an ammonium monohydrogen phosphate solution.
And (4) drying until the moisture content is lower than 0.5%, screening by adopting a 225-mesh sieve, removing iron by adopting an electromagnetic iron remover, and setting the magnetic induction intensity of the electromagnetic iron remover to be 18000 gauss.
The indexes of the finally obtained small-particle nickel hydroxide, cobalt and aluminum hydroxide are as follows:
index (I) Ni+Co+Al P D10 D50 D90
Numerical value 60.9％ 2080ppm 0.51μm 1.38μm 2.09μm
D100 Cd Mg Na Mn Ca
4.18μm 3.8ppm 2.7ppm 6.9ppm 5.9ppm 2.9ppm
K Zn Cu Ti Pb Si
2.9ppm 2.9ppm 0.9ppm 4.8ppm 2.9ppm 5.9ppm
Tap density Sulfate radical Chloride ion BET pH Morphology of
1.57g/mL 12.9ppm 10.8ppm 6.8m2/g 6.95 Spherical shape
The indices of the positive electrode material of nickel cobalt lithium aluminate obtained by mixing and sintering the products obtained in examples 1, 2, and 3 with lithium carbonate are as follows
The lithium nickel cobalt aluminate with small grain diameter is doped with the lithium nickel cobalt manganese with the grain diameter of 15-20 mu m, and the mixture is uniformly mixed:
Figure GDA0002196907240000102
according to the preparation method, the small-particle-size lithium nickel cobalt aluminate prepared from the small-particle-size nickel cobalt aluminum hydroxide is doped with the nickel cobalt lithium manganate with the particle size of 15-20 microns, so that the compaction density of the positive electrode material can be obviously improved.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (7)

1. A preparation method of small-particle nickel cobalt aluminum hydroxide is characterized by comprising the following steps:
(1) preparing a solution, mixing and dissolving nickel, cobalt and aluminum salts into pure water to obtain a nickel, cobalt and aluminum mixed solution, adding an acid-alkali solution to adjust the pH of the mixed solution to 1.0-1.2, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then putting the mixed solution into a constant temperature tank to keep the temperature at 30-35 ℃; adding pure water into ammonium bicarbonate for dissolving, then removing iron through a fluid iron remover, performing precise filtration through a precise filter, and then placing the solution into a constant temperature tank to be constant in temperature to be 30-35 ℃; adding ammonium monohydrogen phosphate into pure water for dissolving, then removing iron through a fluid iron remover, performing precision filtration through a precision filter, and then putting the mixture into a constant temperature tank to keep the temperature at 30-35 ℃;
(2) reacting, namely adding the mixed solution obtained in the step (1), an ammonium bicarbonate solution and an ammonium monohydrogen phosphate solution into a base solution in a cocurrent manner, stabilizing the flow rate of the mixed solution and the flow rate of the ammonium monohydrogen phosphate solution, adjusting the flow rate of the ammonium bicarbonate solution to maintain the pH value of 6-6.5 in the reaction process, keeping the time for adding the materials for 60-90min, maintaining the temperature of 35-40 ℃ in the feeding process, meanwhile, the stirring speed is 250-350r/min, after the materials are added, simultaneously heating to 50-60 deg.C, maintaining the temperature, adding hydrogen peroxide and ammonium bicarbonate solution dropwise, maintaining pH at 6-6.5, reacting for 10-30min, then carrying out solid-liquid separation to obtain a first filter residue and a first filtrate, adding hot pure water into the first filter residue for washing until the conductivity of washing water is less than or equal to 100 mu S/cm;
(3) precipitating and converting, namely adding the first filter residue washed in the step (2) into a polyolefin hyperdispersant solution for slurrying, wherein the mass ratio of the first filter residue to the polyolefin hyperdispersant solution is 1:5-10, heating to 40-50 ℃ after slurrying, keeping the temperature constant, then adding ammonia water into the slurried material, maintaining the pH value of the dropwise adding process to be 7.5-8.0, heating to 75-85 ℃ after adding, stirring for reacting for 30-40min, performing solid-liquid separation to obtain a second filter residue and a second filtrate, and adding the second filter residue into hot pure water washing water to ensure that the conductivity is not more than 20 mu S/cm;
(4) and (4) drying the second filter residue washed in the step (3) by using a disc type dryer, and then screening, removing iron and mixing to obtain small-particle nickel cobalt aluminum hydroxide.
2. The method for preparing small particles of nickel, cobalt and aluminum hydroxide according to claim 1, wherein the method comprises the following steps: the purity of the nickel cobalt aluminum salt in the step (1) is battery grade, the total mole number of the finally obtained nickel cobalt aluminum mixed solution is 1.5-2mol/L, the concentration of ammonium bicarbonate is 0.5-0.6mol/L, the concentration of ammonium monohydrogen phosphate is 1-1.2mol/L, a ceramic filter element is adopted by the precision filter, and the aperture of the ceramic filter element is 20-100 nm.
3. The method for preparing small particles of nickel, cobalt and aluminum hydroxide according to claim 1, wherein the method comprises the following steps: the concentration of ammonium monohydrogen phosphate in the base solution in the step (2) is 0.1-0.12mol/L, meanwhile, the ammonium bicarbonate solution is added to ensure that the pH of the base solution is 6-6.5, the volume of the base solution is 1/15-1/12 of the total volume of the added mixed solution, the ammonium bicarbonate solution and the ammonium monohydrogen phosphate solution, the mixed solution and the ammonium monohydrogen phosphate solution are uniformly added into the base solution, the molar ratio of nickel cobalt aluminum in the mixed solution to the total molar number of ammonium monohydrogen phosphate in the ammonium monohydrogen phosphate solution is maintained to be 3:2.1-2.15, the mass fraction of the added hydrogen peroxide is 25-30%, and the molar number of the added hydrogen peroxide is 2-2.5 times of the total molar number of nickel cobalt ions in the mother solution after the feeding is finished.
4. The method for preparing small particles of nickel, cobalt and aluminum hydroxide according to claim 1, wherein the method comprises the following steps: and (3) in the step (2), the temperature of hot pure water used for washing the first filter residue is 70-75 ℃, the first filtrate is mixed with washing water for washing the first filter residue, an acid solution is added to adjust the pH of the solution to be 2-3, TBP is added to perform extraction, phosphoric acid is extracted, ammonia water is added to perform washing and recovery to obtain ammonium phosphate, and raffinate is concentrated, evaporated and crystallized to obtain ammonium salt.
5. The method for preparing small particles of nickel, cobalt and aluminum hydroxide according to claim 1, wherein the method comprises the following steps: in the step (3), the concentration of the polyolefin hyperdispersant solution is 0.01-0.02%, the stirring speed during slurrying is 300-.
6. The method for preparing small particles of nickel, cobalt and aluminum hydroxide according to claim 1, wherein the method comprises the following steps: and (3) mixing the second filtrate with washing water for washing the second filter residue, adding ammonia water to adjust the pH to 7.5-8, performing precise filtration, concentrating and crystallizing to obtain ammonium monohydrogen phosphate, and returning the solution to obtain an ammonium monohydrogen phosphate solution.
7. The method for preparing small particles of nickel, cobalt and aluminum hydroxide according to claim 1, wherein the method comprises the following steps: and (4) drying until the moisture content is lower than 0.5%, screening by adopting a 225-mesh sieve, removing iron by adopting an electromagnetic iron remover, wherein the magnetic induction intensity of the electromagnetic iron remover is 15000-25000 gauss.
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