CN118289843B - Positive electrode material precursor, preparation method, preparation device and use method thereof - Google Patents

Abstract

The present application discloses a positive electrode material precursor and a preparation method, a preparation device and a use method thereof, and relates to the field of electrode material technology. A method for preparing a positive electrode material precursor, the steps of which include: reagent preparation, reaction base liquid preparation, coprecipitation and post-treatment. It can prepare a precursor material with a dome structure, which helps to improve the cycle performance of the finished battery. A preparation device for a positive electrode material precursor can be used to prepare a precursor material with excellent performance.

Description

A positive electrode material precursor and its preparation method, preparation device and use method

Technical Field

The present application relates to the technical field of electrode materials, and in particular to a positive electrode material precursor and a preparation method, a preparation device and a use method thereof.

Background Art

The development of new energy vehicles is an inevitable trend. The battery life, performance stability, and whether the battery can be charged and discharged quickly are the hot topics we are concerned about. This requires us to continuously innovate our battery technology and continuously reduce the cost of batteries, which is the main theme of the development of power batteries.

At present, power batteries are mainly lithium iron phosphate batteries and ternary batteries. Ternary batteries have greater room for improvement and modification in terms of driving range. The most important part of ternary batteries is ternary cathode materials, and the precursors of ternary cathode materials affect about 60% of the physical and chemical properties of ternary cathode materials, including structure, morphology, particle size, etc. Lithium-ion power batteries must have high energy density, high rate performance, long battery cycle life, safety, stability and low cost, which are problems that we urgently need to solve. The high energy density requirements of ordinary ternary cathode material precursors, and the increasing nickel content also bring about defects such as decreased cycle life and poor thermal stability.

The cathode material precursor structure prepared according to the currently available cathode material precursor preparation method has great defects. It is very difficult for lithium ions to be extracted and embedded, and cations are easily mixed. The structural defects and uneven doping problems result in unsatisfactory capacity retention and cycle performance of the cathode material after sintering.

Summary of the invention

The purpose of the present application is to provide a positive electrode material precursor and a preparation method thereof, which can prepare a precursor material with a dome structure, thereby helping to improve the cycle performance of the finished battery.

Another object of the present application is to provide a device for preparing a positive electrode material precursor and a method for using the device, which can be used to prepare a precursor material with excellent performance.

The technical solution of this application is as follows:

The present invention provides a method for preparing a positive electrode material precursor, which comprises the following steps:

Reagent preparation: prepare nickel-cobalt-manganese-zirconium salt solution, sodium hydroxide solution and ammonia water respectively and set aside;

Preparation of reaction base liquid: add water to the reaction kettle and stir to increase the temperature, introduce inert gas into the water to replace the dissolved oxygen in the water; then add a mixed reagent consisting of sodium hydroxide, ammonia water and a reducing agent into the water, adjust the ammonia concentration and pH of the system to form a base liquid;

Co-precipitation: Add nickel, cobalt, manganese and zirconium salt solution and sodium hydroxide solution, as well as reducing agent or antioxidant and ammonia water, into a reaction kettle containing base liquid to carry out co-precipitation reaction;

Post-treatment: After the coprecipitation reaction is completed, the reacted materials are washed with sodium hydroxide and water respectively, and then dried to obtain the finished precursor material.

Furthermore, in some embodiments of the present application, in the above-mentioned reagent preparation step, the zirconium content in the nickel-cobalt-manganese-zirconium salt solution is 1500-3000 ppm, and the total metal ion concentration in the remaining metal salt solutions is 1-2.5 mol/L; the concentration of the sodium hydroxide solution is 4-10 mol/L; and the concentration of the ammonia water is 5.5-11.5 mol/L.

Furthermore, in some embodiments of the present application, in the above-mentioned reaction base liquid preparation step, water is added to the reaction kettle and stirred and heated to 55-65° C., and an inert gas is introduced into the water for more than 4 hours to replace the dissolved oxygen in the water.

Furthermore, in some embodiments of the present application, in the above-mentioned reaction base liquid preparation step, the linear speed of the stirring speed is 6-10 m/s.

Furthermore, in some embodiments of the present application, in the above reaction base solution preparation step, the ammonia concentration of the system is adjusted to 0.3-0.6 mol/L; the pH of the system is adjusted to 10.5-12 /45°C.

Furthermore, in some embodiments of the present application, in the above-mentioned co-precipitation step, when the co-precipitation reaction is carried out: the first 30 minutes after the start of the reaction is the nucleation stage, during which the ammonia concentration of the system is controlled to be 0.3-0.6 mol/L, and the pH is 10.5-12 /45°C; after 30 minutes of reaction, it enters the growth stage, during which the ammonia concentration of the system is controlled to be 0.3-0.6 mol/L, and the pH is 10.0-11.5 /45°C; after the co-precipitation reaction, the material particle size D50 is 3-12μm.

Furthermore, in some embodiments of the present application, in the above-mentioned post-treatment step, after the coprecipitation reaction is completed, the reacted material is first rinsed with a sodium hydroxide solution with a concentration of 1 to 3 mol/L and a temperature of 65 to 85°C for 30 to 60 minutes, and then rinsed with water at 65 to 85°C for 4 to 5 times.

The embodiment of the present application also provides a positive electrode material precursor, which is prepared by the above preparation method; it can be used to prepare positive electrode materials and batteries; its molecular formula is: Ni _x Co _y Mn _z Zr _p (OH) ₂ , wherein x+y+z+p=1, and 0.2≤x≤0.85, 0.05≤y≤0.4, 0.05≤z≤0.4, and it has a dome structure in microscopic morphology and zirconium is doped in the dome structure.

In the above embodiment, the dome structure is beneficial to improving the compactness and stability of the structure.

The embodiment of the present application also provides a device for preparing a positive electrode material precursor, which is used to prepare the positive electrode material precursor mentioned above;

The device comprises a first reactor, a second reactor and a concentrator; the first reactor is connected to the second reactor via a pipeline, the feed port of the concentrator is connected to the second reactor via a pipeline, and the discharge port of the concentrator is connected to the first reactor via a pipeline.

The present application also provides a method for using the above device, which comprises the following steps:

Reagent preparation: prepare nickel-cobalt-manganese-zirconium salt solution, sodium hydroxide solution and ammonia water respectively and set aside;

Preparation of reaction base liquid: adding water to the first reaction kettle and stirring to increase the temperature, introducing inert gas into the water to replace the dissolved oxygen in the water; then adding a mixed reagent consisting of sodium hydroxide, ammonia water and a reducing agent into the water, adjusting the ammonia concentration and pH of the system to form a base liquid;

Co-precipitation: the first reaction kettle is opened and charged with materials, and nickel-cobalt-manganese-zirconium salt solution and sodium hydroxide solution, as well as reducing agent or antioxidant and ammonia water are simultaneously charged into the first reaction kettle filled with the base liquid to carry out a co-precipitation reaction;

When the material in the first reactor overflows into the second reactor, the second reactor is opened to feed the material, and the nickel-cobalt-manganese-zirconium salt solution and the sodium hydroxide solution, as well as the reducing agent or antioxidant and ammonia water are fed into the second reactor to react;

When the material in the second reactor reaches 2/3 of the volume of the reactor, the material in the second reactor is sent to the concentrator for concentration, and the concentrated material is re-added to the first reactor to form a cycle until the particle size D50 of the material in the first reactor reaches 3-12 μm, and the material is discharged;

Post-treatment: The material discharged from the first reactor after the coprecipitation step is washed with sodium hydroxide and water respectively, and then dried to obtain a finished precursor material.

Furthermore, in some embodiments of the present application, in the above-mentioned co-precipitation step, after the above-mentioned second reactor is opened for feeding, the ammonia concentration of the system in the above-mentioned second reactor is maintained at 0.4-0.6 mol/L, the pH is between 11-12/45°C, and air is introduced above the liquid.

Compared with the prior art, the embodiments of the present application have at least the following advantages or beneficial effects:

The embodiments of the present application provide a positive electrode material precursor and a preparation method, a preparation device and a use method thereof. The prepared precursor material has a unique zirconium-doped dome structure, which is beneficial to improving the compactness and structural stability of the structure, and can effectively improve the transmission efficiency of lithium ions; it can avoid catastrophic collapse of grain boundaries in the material as charging and discharging proceed during the use of the material.

During the preparation process, by controlling the amount of reagents, the formation of crystal nuclei and their crystallinity can be controlled, and the grain growth can be arranged to form a dome structure. Because the dome structure is arranged regularly and orderly to a certain extent, it has good load-bearing performance and resistance to force and torsion, can inhibit the collapse of grain boundaries in the secondary sphere, and at the same time increase the diffusion rate of lithium ions, which is conducive to the diffusion and deintercalation of lithium ions; at the same time, the doped zirconium is evenly distributed in the dome structure, which can effectively improve the cycle performance, so that the positive electrode material has good cycle performance, rate performance and capacity retention rate.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

FIG1 is a schematic structural diagram of a device for preparing a cathode material precursor provided in the present application;

FIG2 is a schematic diagram of the dome structure in an embodiment of the present application;

FIG3 is an electron microscope photograph of the appearance of the product precursor material in Example 4 of the present application.

Figure numerals: 1-first reactor, 2-second reactor, 3-concentrator.

DETAILED DESCRIPTION

In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

It should be noted that relational terms such as "first" and "second" are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the term "comprises" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprises..." do not exclude the existence of other identical elements in the process, method, article or device including the above elements.

It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application may be combined with each other.

The features and performance of the present application are further described in detail below in conjunction with the embodiments.

Example 1

As shown in FIG1 , this embodiment provides a device for preparing a positive electrode material precursor, which includes a first reactor 1, a second reactor 2 and a concentrator 3; the first reactor 1 is connected to the second reactor 2 through a pipeline, the feed port of the concentrator 3 is connected to the second reactor 2 through a pipeline, and the discharge port of the concentrator 3 is connected to the first reactor 1 through a pipeline.

Example 2

This embodiment provides a positive electrode material precursor, which is prepared using the device provided in Embodiment 1 (as shown in FIG1 ), and the preparation method thereof is as follows:

Reagent preparation: prepare nickel-cobalt-manganese-zirconium salt solution with a metal ion concentration of 2.5 mol/L, sodium hydroxide solution with a concentration of 10 mol/L, and ammonia water with a concentration of 11.5 mol/L respectively and set aside;

Preparation of reaction bottom liquid: add start-up pure water to the first reaction kettle 1 to the overflow port, start stirring to ensure a linear velocity of 10 m/s, raise the temperature to 65°C, and introduce nitrogen into the water for more than 4 hours to replace the dissolved oxygen in the water; then add a mixed reagent consisting of sodium hydroxide, ammonia water and a reducing agent to the water, adjust the ammonia concentration of the system to 0.6 mol/L, and the pH to 11-12/45°C to form a bottom liquid;

The first reaction kettle 1 is opened to add materials, and nickel-cobalt-manganese-zirconium salt solution and sodium hydroxide solution, as well as reducing agent or antioxidant and ammonia water are simultaneously added into the first reaction kettle 1 filled with the base liquid to carry out a coprecipitation reaction;

When carrying out co-precipitation reaction: the first 30 minutes after the start of the reaction is the nucleation stage, during which the ammonia concentration of the system is controlled to be 0.6 mol/L and the pH is 11-12 /45°C; after 30 minutes of reaction, it enters the growth stage, during which the ammonia concentration of the system is controlled to be 0.6 mol/L and the pH is 10.0-11 /45°C; during the growth process, Mn ³⁺ is controlled to obey a normal distribution, and the reaction is carried out until the material particle size D50 is 3-12μm.

During the process, when the material in the first reactor 1 overflows into the second reactor 2, the second reactor 2 is opened to feed the material, and the nickel-cobalt-manganese-zirconium salt solution and the sodium hydroxide solution, as well as the reducing agent or antioxidant and the ammonia water are fed into the second reactor 2 for reaction;

When the material in the second reactor 2 reaches 2/3 of the volume of the reactor, the material in the second reactor 2 is sent to the concentrator 3 for concentration, and the concentrated material is re-added to the first reactor 1 to form a cycle until the particle size D50 of the material in the first reactor 1 reaches 3-12 μm, and the material is discharged;

Post-treatment: The material discharged from the first reactor 1 after the co-precipitation step is placed in a centrifuge, first washed with 3 mol/L sodium hydroxide at 85°C for 60 min, then washed with 85°C pure water for 4 to 5 times, controlling Na<100 ppm and S<1000 ppm in the material, and then placed in a 115°C oven for drying to make _H2O <0.5% in the material, to obtain a finished precursor material with a dome structure; the morphology of the dome structure is shown in FIG2 .

As shown in FIG2 , the precursor material has a dome-shaped structure. The dome structure enables the force direction of the material to be the same as the arrow in FIG2 pointing toward the inside of the material, thereby making the physical structure of the product precursor material more stable.

Example 3

This embodiment provides a positive electrode material precursor, which is prepared using the device provided in Embodiment 1 (as shown in FIG1 ), and the preparation method thereof is as follows:

Reagent preparation: prepare nickel-cobalt-manganese-zirconium salt solution with a metal ion concentration of 1.5 mol/L, sodium hydroxide solution with a concentration of 4 mol/L, and ammonia water with a concentration of 5.5 mol/L respectively and set aside;

Preparation of reaction bottom liquid: add start-up pure water to the first reaction kettle 1 to the overflow port, start stirring to ensure a linear velocity of 6 m/s, raise the temperature to 60°C, and introduce nitrogen into the water for more than 4 hours to replace the dissolved oxygen in the water; then add a mixed reagent consisting of sodium hydroxide, ammonia water and a reducing agent to the water, adjust the ammonia concentration of the system to 0.6 mol/L, and the pH to 10-11/45°C to form a bottom liquid;

The first reaction kettle 1 is opened to add materials, and nickel-cobalt-manganese-zirconium salt solution and sodium hydroxide solution, as well as reducing agent or antioxidant and ammonia water are simultaneously added into the first reaction kettle 1 filled with the base liquid to carry out a coprecipitation reaction;

When carrying out co-precipitation reaction: the first 30 minutes after the start of the reaction is the nucleation stage, during which the ammonia concentration of the system is controlled to be 0.6 mol/L and the pH is 11-12 /45°C; after 30 minutes of reaction, it enters the growth stage, during which the ammonia concentration of the system is controlled to be 0.6 mol/L and the pH is 10.0-11 /45°C; during the growth process, Mn ³⁺ is controlled to obey a normal distribution, and the reaction is carried out until the material particle size D50 is 3-12μm.

During the process, when the material in the first reactor 1 overflows into the second reactor 2, the second reactor 2 is opened to feed the material, and the nickel-cobalt-manganese-zirconium salt solution and the sodium hydroxide solution, as well as the reducing agent or antioxidant and the ammonia water are fed into the second reactor 2 for reaction;

When the material in the second reactor 2 reaches 2/3 of the volume of the reactor, the material in the second reactor 2 is sent to the concentrator 3 for concentration, and the concentrated material is re-added to the first reactor 1 to form a cycle until the particle size D50 of the material in the first reactor 1 reaches 3-12 μm, and the material is discharged;

Post-treatment: The material discharged from the first reactor 1 after the co-precipitation step is placed in a centrifuge, first washed with 3 mol/L sodium hydroxide at 85°C for 60 min, then washed with 85°C pure water for 4 to 5 times, controlling Na<100 ppm and S<1000 ppm in the material, and then placed in a 115°C oven for drying to make _H2O <0.5% in the material, to obtain a finished precursor material with a dome structure; the morphology of the dome structure is shown in FIG2 .

Example 4

This embodiment provides a positive electrode material precursor, which is prepared using the device provided in Embodiment 1 (as shown in FIG1 ), and the preparation method thereof is as follows:

Reagent preparation: prepare nickel-cobalt-manganese-zirconium salt solution with a metal ion concentration of 2.0 mol/L, sodium hydroxide solution with a concentration of 10 mol/L, and ammonia water with a concentration of 11.5 mol/L respectively and set aside;

Preparation of reaction bottom liquid: add start-up pure water to the first reaction kettle 1 to the overflow port, start stirring to ensure a linear velocity of 10 m/s, raise the temperature to 60°C, and introduce nitrogen into the water for more than 4 hours to replace the dissolved oxygen in the water; then add a mixed reagent consisting of sodium hydroxide, ammonia water and a reducing agent to the water, adjust the ammonia concentration of the system to 0.6 mol/L, and the pH to 11-12/45°C to form a bottom liquid;

The first reaction kettle 1 is opened to add materials, and nickel-cobalt-manganese-zirconium salt solution and sodium hydroxide solution, as well as reducing agent or antioxidant and ammonia water are simultaneously added into the first reaction kettle 1 filled with the base liquid to carry out a coprecipitation reaction;

When carrying out co-precipitation reaction: the first 30 minutes after the start of the reaction is the nucleation stage, during which the ammonia concentration of the system is controlled to be 0.6 mol/L and the pH is 11-12 /45°C; after 30 minutes of reaction, it enters the growth stage, during which the ammonia concentration of the system is controlled to be 0.6 mol/L and the pH is 10.0-11 /45°C; during the growth process, Mn ³⁺ is controlled to obey a normal distribution, and the reaction is carried out until the material particle size D50 is 3-12μm.

During the process, when the material in the first reactor 1 overflows into the second reactor 2, the second reactor 2 is opened to feed the material, and the nickel-cobalt-manganese-zirconium salt solution and the sodium hydroxide solution, as well as the reducing agent or antioxidant and the ammonia water are fed into the second reactor 2 for reaction;

When the material in the second reactor 2 reaches 2/3 of the volume of the reactor, the material in the second reactor 2 is sent to the concentrator 3 for concentration, and the concentrated material is re-added to the first reactor 1 to form a cycle until the particle size D50 of the material in the first reactor 1 reaches 3-12 μm, and the material is discharged;

Post-treatment: the material discharged from the first reaction kettle 1 after the co-precipitation step is placed in a centrifuge, first washed with 3 mol/L sodium hydroxide at 85°C for 60 min, then washed with 85°C pure water for 4-5 times, controlling Na<100 ppm and S<1000 ppm in the material, and then drying the material in an oven at 115°C to make _H2O <0.5% in the material, to obtain a finished product precursor material with a dome structure; the morphology of the dome structure is shown in FIG2; the appearance and morphology of the product precursor material is shown in FIG3.

The physical and chemical indicators of the finished material are shown in Table 1:

Table 1: Physical and chemical properties of the product materials in Example 4

In summary, the embodiments of the present application provide a positive electrode material precursor and its preparation method, preparation device and use method. The precursor material prepared by the precursor material has a unique zirconium-doped dome structure, which can effectively improve the transmission efficiency of lithium ions; it can avoid the catastrophic collapse of the grain boundaries in the material as the charge and discharge proceed during the use of the material. During the preparation process, by controlling the amount of reagents, the formation of the crystal nucleus can be controlled, its crystallinity can be controlled, and the grain growth can be arranged to form a dome structure. Because the dome structure is arranged regularly and orderly to a certain extent, it has good load-bearing performance and resistance to force and torsion, and can inhibit the collapse of the grain boundaries in the secondary sphere, while increasing the lithium ion diffusion rate, which is conducive to the diffusion and deintercalation of lithium ions; at the same time, the doped zirconium is evenly distributed in the dome structure, which can effectively improve the cycle performance, so that the positive electrode material has good cycle performance, rate performance and capacity retention rate.

The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents the selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present application.

Claims (8)

1. The preparation method of the positive electrode material precursor is characterized by comprising the following steps of:

reagent preparation: respectively preparing nickel cobalt manganese zirconium salt solution, sodium hydroxide solution and ammonia water for later use;

Preparing a reaction base solution: adding water into the reaction kettle, stirring and heating, and introducing inert gas into the water to replace dissolved oxygen in the water; adding a mixed reagent consisting of sodium hydroxide, ammonia water and a reducing agent into water, and regulating the ammonia concentration and pH of the system to form a base solution;

co-precipitation: adding nickel cobalt manganese zirconium salt solution, sodium hydroxide solution, reducing agent or antioxidant and ammonia water into a reaction kettle filled with base solution at the same time to carry out coprecipitation reaction;

Post-treatment: after the coprecipitation reaction is finished, respectively cleaning the reacted materials by using sodium hydroxide and water, and drying to obtain a finished product precursor material;

In the coprecipitation step, when the coprecipitation reaction is carried out: the first 30 min after the reaction starts is a nucleation stage, during which the ammonia concentration of the system is controlled to be 0.3-0.6 mol/L and the pH is controlled to be 10.5-12/45 ℃; after 30 min of reaction, the reaction enters a growth stage, and the ammonia concentration of the system is controlled to be 0.3-0.6 mol/L and the pH value is controlled to be 10.0-11.5/45 ℃; after the coprecipitation reaction, the granularity D50 of the material is 3-12 mu m.

2. The method for preparing a positive electrode material precursor according to claim 1, wherein in the reagent preparation step, the content of zirconium in the nickel-cobalt-manganese-zirconium salt solution is 1500-3000 ppm, and the total metal ion concentration in the rest of the metal salt solution is 1-2.5 mol/L; the concentration of the sodium hydroxide solution is 4-10 mol/L; the concentration of the ammonia water is 5.5-11.5 mol/L.

3. The method for producing a positive electrode material precursor according to claim 1, wherein in the reaction base liquid preparation step, water is added to the reaction vessel and the temperature is raised to 55 to 65 ℃ with stirring, and inert gas is introduced into the water for 4 or more h to replace dissolved oxygen in the water.

4. The method for producing a positive electrode material precursor according to claim 1, wherein in the reaction base liquid preparation step, the ammonia concentration of the system is adjusted to 0.3 to 0.6 mol/L; the pH of the system is regulated to 10.5-12/45 ℃.

5. The method according to claim 1, wherein after the co-precipitation reaction is completed in the post-treatment step, the reacted material is washed with sodium hydroxide solution with a concentration of 1-3 mol/L and a temperature of 65-85 ℃ for 30-60 min and then washed with water with a temperature of 65-85 ℃ for 4-5 times.

6. A positive electrode material precursor, characterized in that it is prepared by the preparation method according to any one of claims 1 to 5; which can be used to prepare positive electrode materials and batteries; the molecular general formula is as follows: ni _xCo_yMn_zZr_p(OH)₂, wherein x+y+z+p=1, and 0.2.ltoreq.x.ltoreq.0.95, 0.05.ltoreq.y.ltoreq. 0.4,0.05.ltoreq.z.ltoreq.0.4, has a dome structure in microscopic morphology and zirconium is doped in the dome structure.

7. A positive electrode material precursor preparing apparatus, characterized in that it is used for preparing the positive electrode material precursor according to claim 6;

The device comprises a first reaction kettle, a second reaction kettle and a concentrator; the first reaction kettle is connected with the second reaction kettle through a pipeline, the feed inlet of the concentrator is connected with the second reaction kettle through a pipeline, and the discharge outlet of the concentrator is connected with the first reaction kettle through a pipeline.

8. A method of using the device of claim 7, comprising the steps of:

reagent preparation: respectively preparing nickel cobalt manganese zirconium salt solution, sodium hydroxide solution and ammonia water for later use;

Preparing a reaction base solution: adding water into the first reaction kettle, stirring and heating, and introducing inert gas into the water to replace dissolved oxygen in the water; adding a mixed reagent consisting of sodium hydroxide, ammonia water and a reducing agent into water, and regulating the ammonia concentration and pH of the system to form a base solution;

co-precipitation: the first reaction kettle is started to feed, nickel cobalt manganese zirconium salt solution, sodium hydroxide solution, reducing agent or antioxidant and ammonia water are simultaneously fed into the first reaction kettle filled with base solution, and coprecipitation reaction is carried out;

when the materials in the first reaction kettle overflow to the second reaction kettle, the second reaction kettle is started to feed materials, and a nickel cobalt manganese zirconium salt solution, a sodium hydroxide solution, a reducing agent or an antioxidant and ammonia water are fed into the second reaction kettle for reaction;

when the material in the second reaction kettle reaches 2/3 of the kettle volume, feeding the material in the second reaction kettle into the concentrator for concentration, and re-feeding the concentrated material into the first reaction kettle to form circulation until the material granularity D50 in the first reaction kettle reaches 3-12 mu m, and discharging the material;

post-treatment: and respectively cleaning the materials discharged from the first reaction kettle after the reaction of the coprecipitation step by using sodium hydroxide and water, and drying to obtain a finished product precursor material.