CN107915263B - Preparation method of small-particle-size ternary cathode material precursor - Google Patents

Preparation method of small-particle-size ternary cathode material precursor Download PDF

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CN107915263B
CN107915263B CN201710772952.9A CN201710772952A CN107915263B CN 107915263 B CN107915263 B CN 107915263B CN 201710772952 A CN201710772952 A CN 201710772952A CN 107915263 B CN107915263 B CN 107915263B
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CN107915263A (en
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郑江峰
吴理觉
文定强
梁伟华
汤依伟
张晨
杨娟
冉建军
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Guangdong Jiana Energy Technology Co Ltd
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Abstract

The invention discloses a preparation method of a small-particle-size ternary positive electrode material precursor, which comprises the following steps of (1) selecting nickel-cobalt-manganese solution as a raw material to prepare a metal mixed salt solution, adding a special reaction base solution into a reaction kettle in advance, and adding the metal salt solution, a complexing agent and a precipitant solution into the reaction kettle in parallel according to a stoichiometric ratio, (2) controlling the particle size of D50 to be 1 ~ 2 mu m when the reaction kettle is full, directly overflowing the mixture to a prepared aging kettle through an overflow pipe after the reaction kettle is full, stopping feeding immediately when the particle size in the reaction kettle is 3.5-4.0 mu m after 10 ~ 20h is long, and (3) washing, sieving and packaging to prepare the small-particle-size ternary precursor with the particle size of 3 ~ 4 mu m.

Description

Preparation method of small-particle-size ternary cathode material precursor
Technical Field
The invention relates to the technical field of nickel-cobalt-manganese ternary materials, in particular to a preparation method of a small-particle-size ternary cathode material precursor.
Background
In 2016, 12 months and 30 days, the ministry of finance, science and technology, Ministry of industry and letter and the development and improvement committee issue a notice about adjusting the policy of popularizing and applying financial subsidies for new energy vehicles, the requirement of the policy of popularizing and applying financial subsidies for new energy vehicles on the energy density of power batteries is higher, enterprises need to adopt more ternary battery systems with higher energy density in order to take more subsidies, and the ternary power batteries come into outbreak in the next year because the state releases the limit on the ternary batteries at the end of the year. The Japanese and Korean enterprises improve the performance of the lithium ion battery by continuously promoting technical progress and developing new materials, always keep the cost performance advantage of the lithium ion battery industry and Chinese products, and occupy the leading position of the high-end lithium ion battery industry. China has a large gap with China such as Japan and Korean, high-end battery products cannot be produced, export products mainly depend on the cost advantage, particularly, the lithium ion battery anode material for the power battery is relatively delayed in development of hot and key fields with great difficulty, lacks of technical support of independent intellectual property rights and does not form industrial scale.
The small-particle-size LiNixCoyMnzO2 positive electrode material has the advantages of stable electrochemical performance, excellent cycle performance, high specific capacity, low cost and the like, and because the particle size is small, the path for lithium ions and electrons to migrate and be removed/embedded from particles is short, and the time is short, so that the small-particle-size ternary material has the advantages of high mass specific capacity, good rate capability and the like.
The small-particle size ternary precursor prepared by a coprecipitation method is mainly roasted into a single crystal ternary material and used for manufacturing a high-voltage lithium battery; the material can also be sintered into a mixture of common polycrystalline ternary materials and large-particle-size ternary materials to improve the material compaction density and increase the volume specific capacity of the material; the ternary battery material with high specific capacity can be manufactured, and the characteristic of high multiplying power of the ternary battery material is utilized to be used for starting power supplies of power automobiles and the like. The small-particle-size ternary precursor crystal nucleus in the current market has the problems of poor sphericity, poor particle size distribution control, void phenomenon in the center and low tap density, so that the material has the problems of poor cycle performance, poor stability, easiness in self-discharge, small specific capacity, low safety performance of a high-voltage power battery and the like, and the small-particle-size material cannot be better applied.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a small-particle-size ternary cathode material precursor, which has the characteristics of good crystal structure integrity, good sphericity, good cyclicity, simple process operation, continuous production, greenness and energy conservation.
The invention can be realized by the following technical scheme:
the invention discloses a preparation method of a small-particle-size ternary cathode material precursor, which comprises the following steps of:
(1) selecting a nickel-cobalt-manganese solution as a raw material, preparing a metal mixed salt solution, adding a special reaction base solution into a reaction kettle in advance, and adding the metal salt solution, a complexing agent and a precipitator solution into the reaction kettle in parallel according to a stoichiometric ratio, wherein the temperature is controlled at 20 ~ 60 ℃, the pH is controlled at 11 ~ 12, the rotating speed is 200 ~ 500r/min, and the whole reaction is carried out under the protection of N2;
(2) the grain size of the first full D50 is controlled to be 1 ~ 2 mu m, when the reaction kettle is full, the reaction kettle directly overflows to a prepared aging kettle through an overflow pipe, the grain size in the reaction kettle is 3.5-4.0 mu m after 10 ~ 20h, and the feeding is immediately stopped;
(3) then uniformly mixing the slurry of the reaction kettle and the slurry of the aging kettle, stirring for 30min, washing by a centrifuge, spin-drying, adding into an oven, drying at 150 ℃, sieving by a 200-mesh sieve and packaging to prepare a ternary precursor with a small particle size of 3 ~ 4 mu m, spherical or quasi-spherical particles with uniform appearance and no caking powder;
the chemical general formula of the small-particle-size ternary precursor is NixCoyMnz (OH)2Wherein x is more than or equal to 0.3 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.4, z is more than or equal to 0.05 and less than or equal to 0.4, and x + y + z =1.
Further, the nickel-cobalt-manganese solution is selected from nickel solution, cobalt solution and manganese solution, the concentration is controlled to be 1.0mol/L ~ 3mol/L, and the temperature of the feed liquid is controlled to be 20-60 ℃.
Furthermore, the complexing agent is ammonia water with the concentration of 2mol/L ~ 10mol/L, and the precipitator is sodium hydroxide solution with the concentration of 2mol/L ~ 10 mol/L.
Further, the pure water and soluble ammonium are mixed to form reaction base solution, the concentration of the soluble ammonium is 3-10g/L, and the temperature of the base solution is 20 ~ 60 ℃.
Furthermore, the soluble ammonium is a mixture of two of ammonia water, ammonium sulfate, ammonium oxalate and ammonium citrate.
Further, the reaction system was brought to a constant pH by adjusting the rate of addition of the alkali solution, and the pH was controlled to 10.5 ~ 11.
The preparation method of the small-particle-size ternary cathode material precursor has the following beneficial technical effects:
the invention provides a continuous feeding process for controlling the particle size distribution of a ternary material, reducing the residual alkali content on the surface of the material, improving the integrity of a crystal structure and improving the cycle performance of the material.
Secondly, the invention provides a unique continuous feeding production mode, a base solution consisting of soluble ammonium and pure water is used for continuous feeding under the drive of high-speed stirring, the system adopts on-line pH control to prepare a precursor with a small grain size of 3 ~ 4 microns, the grain size D50 of a full kettle can be controlled to be 1 ~ 2 microns, and the grain size of a stopped kettle can be accurately controlled to be 3.5 ~ 4.0.0 microns, so that the finished product has no undersized particles, the grain size distribution is less than 1.0, the prepared crystal nucleus has good sphericity and good cyclicity, can meet the requirements of a power battery, and has the advantages of high tap density, good service performance, simple process operation, continuous production, easy ammonia nitrogen recovery and treatment in wastewater, environmental protection and energy conservation.
Drawings
FIG. 1 shows 3. mu. mNi prepared in application example 1 of the present invention0.5Co0.2Mn0.3(OH)2A precursor SEM photograph;
FIG. 2 shows 3. mu. mNi prepared in application example 1 of the present invention0.5Co0.2Mn0.3(OH)2A precursor XRD spectrum;
FIG. 3 shows 3. mu. mNi prepared in example 2 of the present invention0.8Co0.1Mn0.1(OH)2A precursor SEM photograph;
FIG. 4 shows 3. mu. mNi prepared in application example 2 of the present invention0.8Co0.1Mn0.1(OH)2And (3) a precursor XRD spectrum.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following detailed description is provided for the product of the present invention with reference to the examples.
Example 1
The invention discloses a preparation method of a small-particle-size ternary cathode material precursor, which comprises the following steps of:
(1) selecting a nickel-cobalt-manganese solution as a raw material, preparing a metal mixed salt solution, adding a special reaction base solution into a reaction kettle in advance, and adding the metal salt solution, a complexing agent and a precipitator solution into the reaction kettle in parallel according to a stoichiometric ratio; controlling the temperature at 60 ℃; controlling the pH value to be 11.5; the rotating speed is 200 r/min; the whole reaction is carried out in N2Under protection;
(2) controlling the grain diameter of the first full D50 to be 1 ~ 2 mu m, directly overflowing the first full D50 to a prepared aging kettle through an overflow pipe after the reaction kettle is full, and stopping feeding immediately after the grain size in the reaction kettle is 3.5-4.0 mu m after the reaction kettle is 20 hours;
(3) then uniformly mixing the slurry of the reaction kettle and the slurry of the aging kettle, stirring for 30min, washing by a centrifuge, spin-drying, adding into an oven, drying at 150 ℃, sieving by a 200-mesh sieve and packaging to prepare a ternary precursor with a small particle size of 3 ~ 4 mu m, spherical or quasi-spherical particles with uniform appearance and no caking powder;
the chemical general formula of the small-particle-size ternary precursor is NixCoyMnz (OH)2Wherein x is more than or equal to 0.3 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.4, z is more than or equal to 0.05 and less than or equal to 0.4, and x + y + z =1.
In this embodiment, the nickel-cobalt-manganese solution is selected from nickel solution, cobalt solution, and manganese solution, the concentration is controlled to be 1.0mol/L ~ 3mol/L, the temperature of the feed liquid is controlled to be 60 ℃, the complexing agent is selected from ammonia water, the concentration is 10mol/L, the precipitant is sodium hydroxide solution, the concentration is 6mol/L, the pure water and soluble ammonium are mixed to form a reaction base solution, the concentration of the soluble ammonium is 3-g/L, the temperature of the base solution is 60 ℃, the soluble ammonium is selected from two mixtures of ammonia water and ammonium sulfate, the reaction system is at a constant pH value by adjusting the adding speed of the alkali solution, and the pH value is controlled to be 10.5 ~ 11.
Example 2
The invention discloses a preparation method of a small-particle-size ternary cathode material precursor, which comprises the following steps of:
(1) selecting a nickel-cobalt-manganese solution as a raw material, preparing a metal mixed salt solution, adding a special reaction base solution into a reaction kettle in advance, and adding the metal salt solution, a complexing agent and a precipitator solution into the reaction kettle in parallel according to a stoichiometric ratio; controlling the temperature at 40 ℃; controlling the pH value to be 11; the rotating speed is 500 r/min; the whole reaction is carried out under the protection of N2;
(2) controlling the grain diameter of the first full D50 to be 1 ~ 2 mu m, directly overflowing the first full D50 to a prepared aging kettle through an overflow pipe after the reaction kettle is full, and stopping feeding immediately after the grain size in the reaction kettle is 3.5-4.0 mu m after 15 h;
(3) then uniformly mixing the slurry of the reaction kettle and the slurry of the aging kettle, stirring for 30min, washing by a centrifuge, spin-drying, adding into an oven, drying at 150 ℃, sieving by a 200-mesh sieve and packaging to prepare a ternary precursor with a small particle size of 3 ~ 4 mu m, spherical or quasi-spherical particles with uniform appearance and no caking powder;
the chemical general formula of the small-particle-size ternary precursor is NixCoyMnz (OH)2Wherein x is more than or equal to 0.3 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.4, z is more than or equal to 0.05 and less than or equal to 0.4, and x + y + z =1.
In this embodiment, the nickel-cobalt-manganese solution is selected from nickel solution, cobalt solution, and manganese solution, the concentration is controlled to be 1.0mol/L ~ 3mol/L, the temperature of the feed liquid is controlled to be 40 ℃, the complexing agent is selected from ammonia water, the concentration is 2mol/L, the precipitant is sodium hydroxide solution, the concentration is 10mol/L, the pure water and soluble ammonium are mixed to form a reaction base solution, the concentration of the soluble ammonium is 7g/L, the temperature of the base solution is 20 ~ 60 ℃, the soluble ammonium is selected from two mixtures of ammonium oxalate and ammonium citrate, the reaction system is at a constant pH value by adjusting the addition speed of the alkali solution, and the pH value is controlled to be 10.5 ~ 11.
Example 3
The invention discloses a preparation method of a small-particle-size ternary cathode material precursor, which comprises the following steps of:
(1) selecting a nickel-cobalt-manganese solution as a raw material, preparing a metal mixed salt solution, adding a special reaction base solution into a reaction kettle in advance, and adding the metal salt solution, a complexing agent and a precipitator solution into the reaction kettle in parallel according to a stoichiometric ratio; controlling the temperature at 20 ℃; controlling the pH value to be 12; the rotating speed is 350 r/min; the whole reaction is carried out under the protection of N2;
(2) controlling the grain diameter of the first full D50 to be 1 ~ 2 mu m, directly overflowing the first full D50 to a prepared aging kettle through an overflow pipe after the reaction kettle is full, and stopping feeding immediately when the grain size in the reaction kettle is 3.5-4.0 mu m after 10 h;
(3) then uniformly mixing the slurry of the reaction kettle and the slurry of the aging kettle, stirring for 30min, washing by a centrifuge, spin-drying, adding into an oven, drying at 150 ℃, sieving by a 200-mesh sieve and packaging to prepare a ternary precursor with a small particle size of 3 ~ 4 mu m, spherical or quasi-spherical particles with uniform appearance and no caking powder;
the chemical general formula of the small-particle-size ternary precursor is NixCoyMnz (OH)2Wherein x is more than or equal to 0.3 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.4, z is more than or equal to 0.05 and less than or equal to 0.4, and x + y + z =1.
In this embodiment, the nickel-cobalt-manganese solution is selected from nickel solution, cobalt solution, and manganese solution, the concentration is controlled to be 1.0mol/L ~ 3mol/L, the temperature of the feed solution is controlled to be 20 ℃, the complexing agent is selected from ammonia water, the concentration is 10mol/L, the precipitant is sodium hydroxide solution, the concentration is 6mol/L, the pure water and soluble ammonium are mixed to form a reaction base solution, the concentration of the soluble ammonium is 3g/L, the temperature of the base solution is 20 ~ 60 ℃, the soluble ammonium is selected from two mixtures of ammonia water and ammonium oxalate, the reaction system is at a constant pH value by adjusting the addition speed of the alkali solution, and the pH value is controlled to be 10.5 ~ 11.
Example 4
The invention discloses a preparation method of a small-particle-size ternary cathode material precursor, which comprises the following steps of:
(1) selecting a nickel-cobalt-manganese solution as a raw material, preparing a metal mixed salt solution, adding a special reaction base solution into a reaction kettle in advance, and adding the metal salt solution, a complexing agent and a precipitator solution into the reaction kettle in parallel according to a stoichiometric ratio, wherein the temperature is controlled at 20 ~ 60 ℃, the pH is controlled at 11 ~ 12, the rotating speed is 200 ~ 500r/min, and the whole reaction is carried out under the protection of N2;
(2) the grain size of the first full D50 is controlled to be 1 ~ 2 mu m, when the reaction kettle is full, the reaction kettle directly overflows to a prepared aging kettle through an overflow pipe, the grain size in the reaction kettle is 3.5-4.0 mu m after 10 ~ 20h, and the feeding is immediately stopped;
(3) then uniformly mixing the slurry of the reaction kettle and the slurry of the aging kettle, stirring for 30min, washing by a centrifuge, spin-drying, adding into an oven, drying at 150 ℃, sieving by a 200-mesh sieve and packaging to prepare a ternary precursor with a small particle size of 3 ~ 4 mu m, spherical or quasi-spherical particles with uniform appearance and no caking powder;
the chemical general formula of the small-particle-size ternary precursor is NixCoyMnz (OH)2Wherein x is more than or equal to 0.3 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.4, z is more than or equal to 0.05 and less than or equal to 0.4, and x + y + z =1.
In this embodiment, the nickel-cobalt-manganese solution is selected from nickel solution, cobalt solution, and manganese solution, the concentration is controlled to be 1.0mol/L ~ 3mol/L, the temperature of the feed liquid is controlled to be 20-60 ℃, the complexing agent is selected from ammonia water with a concentration of 2mol/L ~ 10mol/L, the precipitant is sodium hydroxide solution with a concentration of 2mol/L ~ 10mol/L, the pure water and soluble ammonium are mixed to form a reaction base solution, the concentration of the soluble ammonium is 3-10g/L, the temperature of the base solution is 20 ~ 60 ℃, the soluble ammonium is selected from two mixtures of ammonia water, ammonium sulfate, ammonium oxalate, and ammonium citrate, the reaction system is in a constant pH value by adjusting the adding speed of the alkali solution, and the pH value is controlled to be 10.5 ~ 11.
Application example 1
Preparation of 3 μm Ni by continuous feeding0.5Co0.2Mn0.3(OH)2And (3) a ternary cathode material precursor.
Nickel sulfate solution, cobalt sulfate solution, manganese sulfate solution, sodium hydroxide and ammonia water are adopted as reaction raw materials to respectively prepare 2mol/L nickel cobalt manganese metal salt solution (the ratio of nickel cobalt manganese is 5:2: 3), 8mol/L sodium hydroxide solution and 6mol/L ammonia water at the temperature of 45 ℃.
At 2m3Adding pure water into a pilot scale reaction kettle, adding 6mol/L ammonia solution, ammonium citrate and pure water to mix into stable reaction base solution, wherein the volume of the reaction base solution accounts for 50 percent of the volume of the reaction kettle, stirring for 30min at the rotating speed of 100r/min, and adding 8mol/L sodium hydroxide solution into the base solutionThe pH was adjusted to 12 and the whole reaction was protected by N2.
Then adding the nickel-cobalt-manganese metal salt solution, sodium hydroxide and ammonia water into a reaction kettle in parallel according to a molar ratio of 1:4:2 by using a metering pump, controlling the reaction temperature to be 50 ℃, the rotating speed to be 400r/min and the pH to be 10.5 ~ 11, continuously feeding the reaction, measuring the particle size D50 of the full kettle to be 1.89 mu m after the reaction kettle is full, directly opening an overflow pipe to overflow to a temporary storage kettle until the particle size in the reaction kettle is 3.7 mu m, immediately stopping feeding, mixing aged temporary storage kettle slurry with reaction kettle slurry, stirring for 30min, washing by using alkali liquor and pure water through a centrifuge, drying by spin-drying, adding into an oven to dry at 150 ℃, sieving by using a 200-mesh sieve and packaging, thus preparing the small-particle-size ternary precursor of 3 ~ 4 mu m.
The prepared 3 μm ternary precursor (Ni + Co + Mn) had a chemical content of 62.5%, S =700ppm, particle size distribution Dmin =2.37 μm, D50=3.45 μm, Dmax =4.62 μm, TD =1.75g/cm3,SSA=10.5m2(iv) g, spherical or spheroidal particles in morphology, uniform in appearance, and black powder without agglomeration, corresponding SEM and XRD patterns are shown in fig. 1 and 2.
Application example 2
Preparation of 3 μmNi using continuous feed0.8Co0.1Mn0.1(OH)2And (3) a ternary cathode material precursor.
Prepared 3 μm Ni0.8Co0.1Mn0.1(OH)2The chemical content of the precursor (Ni + Co + Mn) was 62.8%, S =500ppm, the particle size distribution Dmin =2.66 μm, D50=3.16 μm, Dmax =4.75 μm, TD =2.05g/cm3,SSA=9.2m2(g) spherical or spheroidal particles with uniform appearance and no agglomeration, brown yellow powder.
Nickel sulfate hexahydrate, cobalt sulfate heptahydrate, manganese sulfate monohydrate, sodium hydroxide and ammonia water are used as reaction raw materials to respectively prepare 2mol/L nickel cobalt manganese metal salt solution (the ratio of nickel cobalt manganese is 8:1: 1), 8mol/L sodium hydroxide solution and 6mol/L ammonia water at 50 ℃. At 2m3Adding pure water into a pilot scale reaction kettle, adding 6mol/L ammonia solution, ammonium citrate and pure water to obtain stable reaction base solution, wherein the volume of the reaction base solution accounts for 50% of the reaction kettle, and stirring the reaction base solution at the rotating speed of 100r/min for 30%min, add 8mol/L NaOH solution to the base solution to adjust the pH to 11.5, and protect the whole reaction with N2.
Then, the nickel-cobalt-manganese metal salt solution, sodium hydroxide and ammonia water are added into a reaction kettle in a concurrent flow mode according to a molar ratio of 1:4:3 by a metering pump, the reaction temperature is 60 ℃, the rotating speed is controlled to be 400r/min, the pH is controlled to be 10.8 ~ 11, the reaction feeding is continuously carried out, when the reaction kettle is full, the D50 is 1.95 mu m, an overflow pipe is directly opened to overflow to a temporary storage kettle until the particle size in the reaction kettle is 3.5 mu m, the feeding is immediately stopped, then the aged temporary storage kettle slurry and the reaction kettle slurry are mixed, stirred for 30min, washed by alkali liquor and pure water through a centrifuge, dried, added into an oven to be dried at 150 ℃, sieved by a 200-mesh sieve and packaged, and then the ternary precursor with the small particle size of 3 ~ 4 mu m can be prepared, and the corresponding SEM and XRD pattern are shown in figures 3 and 4.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; as will be readily apparent to those skilled in the art from the disclosure herein, the present invention may be practiced without these specific details; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (1)

1. A preparation method of a small-particle-size ternary cathode material precursor is characterized by comprising the following steps of:
(1) selecting nickel-cobalt-manganese solution as raw material, preparing metal mixed salt solution, adding special reaction base liquor into reaction still in advance, adding metal salt solution, complexing agent and precipitant solution according to stoichiometric ratio, parallel-flowing them into reaction still, making the whole reaction be in N reaction2Under protection;
(2) the grain size of the first full D50 is controlled to be 1 ~ 2 mu m, when the reaction kettle is full, the reaction kettle directly overflows to a prepared aging kettle through an overflow pipe, the grain size in the reaction kettle is 3.5-4.0 mu m after 10 ~ 20h, and the feeding is immediately stopped;
(3) then uniformly mixing the slurry of the reaction kettle and the slurry of the aging kettle, stirring for 30min, washing by a centrifuge, spin-drying, adding into an oven, drying at 150 ℃, sieving by a 200-mesh sieve and packaging to prepare a ternary precursor with a small particle size of 3 ~ 4 mu m, spherical or quasi-spherical particles with uniform appearance and no caking powder;
the chemical general formula of the small-particle-size ternary precursor is NixCoyMnz (OH)2Wherein x is more than or equal to 0.3 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.4, z is more than or equal to 0.05 and less than or equal to 0.4, and x + y + z = 1; wherein the content of the first and second substances,
the nickel-cobalt-manganese solution is selected from nickel solution, cobalt solution and manganese solution, the concentration is controlled to be 1.0mol/L ~ 3mol/L, and the temperature of the feed liquid is controlled to be 20-60 ℃;
the complexing agent is ammonia water with the concentration of 2mol/L ~ 10mol/L, and the precipitator is sodium hydroxide solution with the concentration of 2mol/L ~ 10 mol/L;
mixing pure water and soluble ammonium to form reaction base solution, wherein the concentration of the soluble ammonium is 3-10g/L, and the temperature of the base solution is 20 ~ 60 ℃;
the soluble ammonium is a mixture of two of ammonia water, ammonium sulfate, ammonium oxalate and ammonium citrate;
the reaction system was brought to a constant pH value by adjusting the rate of addition of the alkali solution, and the pH value was controlled to 10.5 ~ 11.
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